Spectral-Polarization Properties and Light Resistance of Polyvinyl-Alcohol Films Colored With Disazo Dyes

NASA Astrophysics Data System (ADS)

Fillipovich, L. N.; Ariko, N. G.; Agabekov, V. E.; Malashko, P. M.

2005-09-01

Polarizers containing disazo dyes from the group of azobenzene-azonaphthalene have been developed. It has been established that their polarizing ability is determined by the mutual disposition of the azo group and electron-donor substituents in the naphthalene ring. On diazo coupling of γ acid into the α position relative to the oxy group, the M1 and M3 dyes are formed, the polarizing ability of which in uniaxially oriented polyvinyl-alcohol films is higher than in the M2 dye produced as a result of diazo coupling into the α position relative to the amino group. On irradiation by UV light, the dyes are subjected to photodestruction, which, in the case of M2, proceeds through trans-cis-isomerization. The rate of photodestruction depends on the aggregation of the dye molecules, and it increases in the presence of a free-radical initiator. The UV absorber (substituted benzotriazole) and the uniaxial orientation of the film retard this process.

Comparison of Cu2+ and Zn2+ thermalcatalyst in treating diazo dye

NASA Astrophysics Data System (ADS)

Lau, Y. Y.; Wong, Y. S.; Ong, S. A.; Lutpi, N. A.; Ho, L. N.

2018-05-01

This research demonstrates the comparison between copper (II) sulphate (CuSO4) and zinc oxide (ZnO) as thermalcatalysts in thermolysis process for the treatment of diazo reactive black 5 (RB 5) wastewater. CuSO4 was found to be the most effective thermalcatalyst in comparison to ZnO. The color removal efficiency of RB 5 catalysed by CuSO4 and ZnO were 91.55 % at pH 9.5 and 7.36 % at pH 2, respectively. From the UV-Vis wavelength scan, CuSO4 catalyst is able to cleave the molecular structure bonding more efficiently compared to ZnO. ZnO which only show a slight decay on the main chemical network strands: azo bond, naphthalene and benzene rings whereas CuSO4 catalyst is able to fragment azo bond and naphthalene more effectively. The degradation reactions of CuSO4 and ZnO as thermalcatalysts in thermolysis process were compared.

A new reactivity mode for the diazo group: diastereoselective 1,3-aminoalkylation reaction of β-amino-α-diazoesters to give triazolines.

PubMed

Kuznetsov, Alexey; Gulevich, Anton V; Wink, Donald J; Gevorgyan, Vladimir

2014-08-18

A novel mode of reactivity for the diazo group, the 1,3-addition of a nucleophile and an electrophile to the diazo group, has been realized in the intramolecular aminoalkylation of β-amino-α-diazoesters to form tetrasubstituted 1,2,3-triazolines. The reaction exhibited a broad scope, good functional group tolerance, and excellent diastereoselectivity. In addition, a new Au-catalyzed intramolecular transannulation reaction of the obtained propargyl triazolines to give pyrroles has been discovered. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimized diazo scaffold for protein esterification.

PubMed

Mix, Kalie A; Raines, Ronald T

2015-05-15

The O-alkylation of carboxylic acids with diazo compounds provides a means to esterify carboxylic acids in aqueous solution. A Hammett analysis of the reactivity of diazo compounds derived from phenylglycinamide revealed that the (p-methylphenyl)glycinamide scaffold has an especially high reaction rate and ester/alcohol product ratio and esterifies protein carboxyl groups more efficiently than any known reagent.

Alkyl halide-free heteroatom alkylation and epoxidation facilitated by a recyclable polymer-supported oxidant for the in-flow preparation of diazo compounds.

PubMed

Nicolle, Simon M; Hayes, Christopher J; Moody, Christopher J

2015-03-16

Highly reactive metal carbenes, generated from simple ketones via diazo compounds, including diazo-amides and -phosphonates, using a recyclable reagent in-flow, are transient but versatile electrophiles for heteroatom alkylation reactions and for epoxide formation. The method produces no organic waste, with the only by-products being water, KI and nitrogen, without the attendant hazards of isolation of intermediate diazo compounds. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimized Diazo Scaffold for Protein Esterification

PubMed Central

Mix, Kalie A.

2015-01-01

The O-alkylation of carboxylic acids with diazo compounds provides a means to esterify carboxylic acids in aqueous solution. A Hammett analysis of the reactivity of diazo compounds derived from phenylglycinamide revealed that the p-methylphenylglycinamide scaffold has an especially high reaction rate and ester:alcohol product ratio, and esterifies protein carboxyl groups more efficiently than does any known reagent. PMID:25938936

α-Diazo oxime ethers for N-heterocycle synthesis.

PubMed

Choi, Subin; Ha, Sujin; Park, Cheol-Min

2017-06-01

This Feature Article introduces the preparation and synthetic utility of α-diazo oxime ethers. α-Oximino carbenes are useful synthons for N-heterocycles, and can be easily prepared from α-diazo oxime ethers as precursors. We begin with the preparation of α-diazo oxime ethers and their application in [3+2] cycloaddition. It turns out that the nature of metals bound to carbenes plays a crucial role in modulating the reactivity of α-oximino carbenes, in which copper carbenes smoothly react with enamines, whereas the less reactive enol ethers and nitriles require gold carbenes. In Section 3.2, a discussion on N-O and C-H bond activation is presented. Carbenes derived from diazo oxime ethers show unique reactivity towards N-O and C-H bond activation, in which the proximity of the two functionalities, carbene and oxime ether, dictates the preferred reaction pathways toward pyridines, pyrroles, and 2H-azirines. In Section 3.3, the development of tandem reactions based on α-diazo oxime ethers is discussed. The nature of carbenes in which whether free carbenes or metal complexes are involved dissects the pathway and forms different types of 2H-azirines. The 2H-azirine formation turned out to be an excellent platform for the tandem synthesis of N-heterocycles including pyrroles and pyridines. In the last section, we describe the electrophilic activation of 2H-azirines with vinyl carbenes and oximino carbenes. The resulting azirinium species undergo rapid ring expansion rearrangements to form pyridines and pyrazines.

Decreasing Distortion Energies without Strain: Diazo-Selective 1,3-Dipolar Cycloadditions.

PubMed

Gold, Brian; Aronoff, Matthew R; Raines, Ronald T

2016-07-15

The diazo group has attributes that complement those of the azido group for applications in chemical biology. Here, we use computational analyses to provide insights into the chemoselectivity of the diazo group in 1,3-dipolar cycloadditions. Dipole distortion energies are responsible for ∼80% of the overall energetic barrier for these reactions. Here, we show that diazo compounds, unlike azides, provide an opportunity to decrease that barrier substantially without introducing strain into the dipolarophile. The ensuing rate enhancement is due to the greater nucleophilic character of a diazo group compared to that of an azido group, which can accommodate decreased distortion energies without predistortion. The tuning of distortion energies with substituents in a diazo compound or dipolarophile can enhance reactivity and selectivity in a predictable manner. Notably, these advantages of diazo groups are amplified in water. Our findings provide a theoretical framework that can guide the design and application of both diazo compounds and azides in "orthogonal" contexts, especially for biological investigations.

Role of dissolved oxygen on the degradation mechanism of Reactive Green 19 and electricity generation in photocatalytic fuel cell.

PubMed

Lee, Sin-Li; Ho, Li-Ngee; Ong, Soon-An; Wong, Yee-Shian; Voon, Chun-Hong; Khalik, Wan Fadhilah; Yusoff, Nik Athirah; Nordin, Noradiba

2018-03-01

In this study, a membraneless photocatalytic fuel cell with zinc oxide loaded carbon photoanode and platinum loaded carbon cathode was constructed to investigate the impact of dissolved oxygen on the mechanism of dye degradation and electricity generation of photocatalytic fuel cell. The photocatalytic fuel cell with high and low aeration rate, no aeration and nitrogen purged were investigated, respectively. The degradation rate of diazo dye Reactive Green 19 and the electricity generation was enhanced in photocatalytic fuel cell with higher dissolved oxygen concentration. However, the photocatalytic fuel cell was still able to perform 37% of decolorization in a slow rate (k = 0.033 h -1 ) under extremely low dissolved oxygen concentration (approximately 0.2 mg L -1 ) when nitrogen gas was introduced into the fuel cell throughout the 8 h. However, the change of the UV-Vis spectrum indicates that the intermediates of the dye could not be mineralized under insufficient dissolved oxygen level. In the aspect of electricity generation, the maximum short circuit current (0.0041 mA cm -2 ) and power density (0.00028 mW cm -2 ) of the air purged photocatalytic fuel cell was obviously higher than that with nitrogen purging (0.0015 mA cm -2 and 0.00008 mW cm -2 ). Copyright © 2017 Elsevier Ltd. All rights reserved.

Isolation, cloning and characterization of an azoreductase from the halophilic bacterium Halomonas elongata.

PubMed

Eslami, Maryam; Amoozegar, Mohammad Ali; Asad, Sedigheh

2016-04-01

Azo dyes are a major class of colorants used in various industries including textile, paper and food. These dyes are regarded as pollutant since they are not readily reduced under aerobic conditions. Halomonas elongata, a halophilic bacterium, has the ability to decolorize different mono and di-azo dyes in anoxic conditions. In this study the putative azoreductase gene of H. elongata, formerly annotated as acp, was isolated, heterologously expressed in Escherichia coli, purified and characterized. The gene product, AzoH, was found to have a molecular mass of 22 kDa. The enzyme requires NADH, as an electron donor for its activity. The apparent Km was 63 μM for NADH and 12 μM for methyl red as a mono-azo dye substrate. The specific activity for methyl red was 0.27 μmol min(-1)mg(-1). The optimum enzyme activity was achieved in 50mM sodium phosphate buffer at pH 6. Although increased salinity resulted in reduced activity, AzoH could decolorize azo dye at NaCl concentrations up to 15% (w/v). The enzyme was also shown to be able to decolorize remazol black B as a representative of di-azo dyes. This is the first report describing the sequence and activity of an azo-reducing enzyme from a halophilic bacterium. Copyright © 2015 Elsevier B.V. All rights reserved.

Part 1: Synthesis and visible absorption spectra of some new monoazo dyes derived from ethyl 2-amino-4-(4";-substitutedphenyl)thiophenes

NASA Astrophysics Data System (ADS)

Babür, Banu; Ertan, Nermin

2014-10-01

Series of monoazo dyes from some ethyl 2-amino-4-(4";-substitutedphenyl) thiophenes were prepared and characterized. The structure of the substances was confirmed by FT-IR, 1H NMR and mass spectroscopic techniques. The relationship among the structure of the dyes, their absorption characteristics and the solvatochromic and halochromic behaviors of the dyes were investigated. Introduction of electron-accepting substituent into the diazo moiety results in large bathochromic shifts in all solvents used. The dyes exhibited positive solvatochromism and their solvatochromic properties were discussed in relation to tautomerism.

Taming hazardous chemistry in flow: the continuous processing of diazo and diazonium compounds.

PubMed

Deadman, Benjamin J; Collins, Stuart G; Maguire, Anita R

2015-02-02

The synthetic utilities of the diazo and diazonium groups are matched only by their reputation for explosive decomposition. Continuous processing technology offers new opportunities to make and use these versatile intermediates at a range of scales with improved safety over traditional batch processes. In this minireview, the state of the art in the continuous flow processing of reactive diazo and diazonium species is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors.

PubMed

Hu, Mingyou; Ni, Chuanfa; Li, Lingchun; Han, Yongxin; Hu, Jinbo

2015-11-18

A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.

Direct Carboxylation of the Diazo Group ipso-C(sp2)-H bond with Carbon Dioxide: Access to Unsymmetrical Diazomalonates and Derivatives.

PubMed

Liu, Qianyi; Li, Man; Xiong, Rui; Mo, Fanyang

2017-12-15

The direct carboxylation of the ipso-C(sp 2 )-H bond of a diazo compound with carbon dioxide under mild reaction conditions is described. This method is transition-metal-free, uses a weak base, and proceeds at ambient temperature under atmospheric pressure in carbon dioxide. The carboxylation exhibits high reactivity and is amenable to subsequent diversification. A series of unsymmetrical 1,3-diester/keto/amide diazo compounds are obtained with moderate to excellent yields (up to 99%) with good functional group compatibility.

Diazo Esters as Dienophiles in Intramolecular (4 + 2) Cycloadditions: Computational Explorations of Mechanism.

PubMed

Duan, Abing; Yu, Peiyuan; Liu, Fang; Qiu, Huang; Gu, Feng Long; Doyle, Michael P; Houk, K N

2017-02-22

The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model. The 1,3-dipolar cycloaddition is strongly favored for the intermolecular system. The intramolecular example is unique because the tether strongly favors the (4 + 2) cycloaddition.

Straightforward Entry toward Highly Substituted 2,3-Dihydrobenz[ b]oxepines by Ring Expansion of Benzopyryliums with Donor-Acceptor Diazo Compounds.

PubMed

Courant, Thibaut; Pasco, Morgane; Lecourt, Thomas

2018-05-04

Ylide-type reactivity of diazo compounds is exploited in a new way to prepare benzo[ b]oxepines thanks to the formation of three chemical bonds and two contiguous and highly substituted stereocenters in a single pot. This cationic reaction cascade first involves addition of a donor-acceptor-substituted diazo compound to a benzopyrylium. Selective 1,2 migration of the endocyclic C-C bond then results in a ring-expansion and generates a second oxocarbenium that is trapped by a nucleophile added sequentially.

Sulfate-reducing mixed communities with the ability to generate bioelectricity and degrade textile diazo dye in microbial fuel cells.

PubMed

Miran, Waheed; Jang, Jiseon; Nawaz, Mohsin; Shahzad, Asif; Lee, Dae Sung

2018-06-15

The biotreatment of recalcitrant wastes in microbial fuel cells (MFCs) rather than chemical, physical, and advanced oxidation processes is a low-cost and eco-friendly process. In this study, sulfate-reducing mixed communities in MFC anodic chamber were employed for simultaneous electricity generation, dye degradation, and sulfate reduction. A power generation of 258 ± 10 mW/m 2 was achieved under stable operating conditions in the presence of electroactive sulfate-reducing bacteria (SRB). The SRBs dominant anodic chambers result in dye, chemical oxygen demand (COD), and sulfate removal of greater than 85% at an initial COD (as lactate)/SO 4 2- mass ratio of 2.0 and dye concentration of 100 mg/L. The effects of the COD/SO 4 2- ratio (5.0:1.0-0.5:1.0) and initial diazo dye concentration (100-1000 mg/L) were studied to evaluate and optimize the MFC performance. Illumina Miseq technology for bacterial community analysis showed that Proteobacteria (89.4%), Deltaproteobacteria (52.7%), and Desulfovibrio (48.2%) were most dominant at phylum, class, and genus levels, respectively, at the MFC anode. Integration of anaerobic SRB culture in MFC bioanode for recalcitrant chemical removal and bioenergy generation may lead to feasible option than the currently used technologies in terms of overall pollutant treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Competition strategies for the decolorization of a textile-reactive dye with the white-rot fungi Trametes versicolor under non-sterile conditions.

PubMed

Libra, Judy A; Borchert, Maren; Banit, Salima

2003-06-20

A variety of white-rot fungi can oxidize textile dyes under sterile conditions; however, an important consideration for their use in treating wastewater containing textile dyes is whether similar degrees of treatment can be achieved under non-sterile conditions. Four strategies were investigated for their potential in optimizing the use of the fungus Trametes versicolor in non-sterile culture for treating wastewater containing the diazo textile dye C.I. Reactive Black 5 (RB5). Three strategies with suspended culture were designed to increase the decolorization activity in suspended culture from a given amount of T. versicolor inoculum based on its tolerance of low pH (pH reduction in medium), production of extracellular enzymes (use of suspended enzymes alone), and its ability to produce enzymes independent of growth (nitrogen limitation in medium). The results showed that reduction of the medium pH to 3 did not suppress bacterial growth, while enzyme production by T. versicolor ceased. The use of the extracellular enzymes alone would allow the decoupling of the process of fungal growth from wastewater treatment; however, the enzyme activity of an enzyme suspension decreased rapidly under non-sterile conditions. The strategy of limiting nitrogen in the medium to suppress bacterial growth has potential together with the fourth strategy, the cultivation of fungi on organic solids to produce inocula for a decolorization process under non-sterile conditions. A high degree of decolorization of RB5 under non-sterile conditions was achieved with T. versicolor grown on grains as sole substrate. The rate of decolorization was dependent on the amount of fungal inoculum used. Copyright 2003 Wiley Periodicals, Inc. Biotechnol Bioeng 82: 736-744, 2003.

Degradation reaction of Diazo reactive black 5 dye with copper (II) sulfate catalyst in thermolysis treatment.

PubMed

Lau, Yen-Yie; Wong, Yee-Shian; Ang, Tze-Zhang; Ong, Soon-An; Lutpi, Nabilah Aminah; Ho, Li-Ngee

2018-03-01

The theme of present research demonstrates performance of copper (II) sulfate (CuSO 4 ) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO 4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO 4 . Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp 2 carbon to form C-C of the sp 3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k 1 is 6.5224 whereas the degradation rate constant with catalyst, k 2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.

Treatment of diazo dye C.I. Reactive Black 5 in aqueous solution by combined process of interior microelectrolysis and ozonation.

PubMed

Guo, Xiaoyan; Cai, Yaping; Wei, Zhongbo; Hou, Haifeng; Yang, Xi; Wang, Zunyao

2013-01-01

Interior microelectrolysis (IM) as a pretreatment process was effective to treat Reactive Black 5 (RB5) in this study. The removal rates of chemical oxygen demand (COD), total organic carbon (TOC) and color were 46.05, 39.99 and 98.77%, respectively, when this process was conducted under the following optimal conditions: the volumetric ratio between iron scraps and active carbon (AC) (V(Fe)/V(C)) 1.0, pH 2.0, aeration dosage 0.6 L/min, and reaction time 100 min. Contaminants could be further removed by ozonation. After subsequent ozonation for 200 min, the solution could be completely decolorized, and the COD and TOC removal rates were up to 77.78 and 66.51%, respectively. In addition, acute toxicity tests with Daphnia magna showed that pretreatment by IM generated effluents that were more toxic when compared with the initial wastewater, and the toxicity was reduced after subsequent ozonation.

Conversion of Azides into Diazo Compounds in Water

PubMed Central

Chou, Ho-Hsuan; Raines, Ronald T.

2013-01-01

Diazo compounds are in widespread use in synthetic organic chemistry, but have untapped potential in chemical biology. We report on the design and optimization of a phosphinoester that mediates the efficient conversion of azides into diazo compounds in phosphate buffer at neutral pH and room temperature. High yields are maintained in the presence of common nucleophilic or electrophilic functional groups, and reaction progress can be monitored by colorimetry. As azido groups are easy to install and maintain in biopolymers or their ligands, this new mode of azide reactivity could have substantial utility in chemical biology. PMID:24053717

Comparative performance of anodic oxidation and electrocoagulation as clean processes for electrocatalytic degradation of diazo dye Acid Brown 14 in aqueous medium.

PubMed

Bassyouni, D G; Hamad, H A; El-Ashtoukhy, E-S Z; Amin, N K; El-Latif, M M Abd

2017-08-05

In this study, a laboratory scale for the treatment of a recalcitrant and toxic synthetic wastewater containing diazo dye, acid brown 14 (AB-14) has been comparatively performed by two electro-catalytic treatment processes, namely anodic oxidation (AO) and electrocoagulation (EC) using a new batch electrochemical cell. Additionally, the influence of several operating parameters such as; current density (j), initial dye concentration (C o ), NaCl concentration (C N ), and pH on the color removal efficiency and chemical oxygen demand (COD) are evaluated. The powerful capability of the AO and EC of AB-14 which related to the mechanistic reaction pathway is shown. The poor degradation is ascribed to higher C o and pH, while the enhancement of j and C N is responsible for better degradation of AB-14 dye. The results indicate that the EC is more effective than AO under the same operational condition. A kinetic model is developed for evaluation of the pseudo-first-order-rate constant (k app ) as a function of various operational parameters. The results emphasize the high efficiency of AO and EC and the clean processes which are hopeful alternative for the treatment of the large volume wastewater of the textile industry. Copyright © 2017 Elsevier B.V. All rights reserved.

Eco-Friendly Synthesis of Some Thiosemicarbazones and Their Applications as Intermediates for 5-Arylazothiazole Disperse Dyes.

PubMed

Gaffer, Hatem E; Khalifa, Mohamed E

2015-12-09

The solid-solid reactions of thiosemicarbazide with 4-formylantipyrine, 2-acetylpyrrole and camphor were performed to afford the thiosemicarbazones 1-3 which underwent hetero-cyclization with phenacyl bromide to furnish the corresponding thiazole derivatives 4-6. The yields of the reactions are quantitative in all cases and the products do not require further purification. A series of 5-arylazo-2-(substituted ylidene-hydrazinyl)-thiazole dyes 7-9 was then prepared by diazo coupling of thiazole derivatives 4-6 with several diazonium chlorides. The synthesized dyes were applied as disperse dyes for dyeing polyester fabric. The dyed fabrics exhibit good washing, perspiration, sublimation and light fastness properties, with little variation in their moderate to good rubbing fastness.

New fluorescent symmetrically substituted perylene-3,4,9,10-dianhydride-azohybrid dyes: Synthesis and spectroscopic studies

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Shabir, Ghulam

2014-12-01

Five phenolic azo-dyes (3a-e) were synthesized by diazo coupling of the suitably substituted anilines (1a-e) with phenol at low temperature in alkaline medium. The resulting dyes have low solubility in aqueous medium due to lack of carboxylic or sulfonic solubilizing functionalities. The hybridization of perylene dianhydride with phenolic azo-dyes was achieved by the nucleophilic aromatic substitution (SNAr) reaction of perylene-3,4,9,10-dianhydride 4 with phenolic azo-dyes 3a-e in basic medium. The hybrid dyes exhibit absorption maxima λmax in the range 440-460 nm in aqueous medium due to presence of azo linkage and highly conjugated system of π bonds. Fluorescence spectra of these dyes in water show sharp emission peaks with small band widths. The structures of perylene-azo dyes were confirmed by FTIR and NMR spectroscopy.

Highly Stereoselective Gold-Catalyzed Coupling of Diazo Reagents and Fluorinated Enol Silyl Ethers to Tetrasubstituted Alkenes.

PubMed

Liao, Fu-Min; Cao, Zhong-Yan; Yu, Jin-Sheng; Zhou, Jian

2017-02-20

We report a highly stereoselective synthesis of all-carbon or fluorinated tetrasubstituted alkenes from diazo reagents and fluorinated enol silyl ethers, using C-F bond as a synthetic handle. Cationic Au I catalysis plays a key role in this reaction. Remarkable fluorine effects on the reactivity and selectivity was also observed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

λ5-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules.

PubMed

Marinozzi, Maura; Pertusati, Fabrizio; Serpi, Michaela

2016-11-23

The compounds characterized by the presence of a λ 5 -phosphorus functionality at the α-position with respect to the diazo moiety, here referred to as λ 5 -phosphorus-containing α-diazo compounds (PCDCs), represent a vast class of extremely versatile reagents in organic chemistry and are particularly useful in the preparation of phosphonate- and phosphinoxide-functionalized molecules. Indeed, thanks to the high reactivity of the diazo moiety, PCDCs can be induced to undergo a wide variety of chemical transformations. Among them are carbon-hydrogen, as well as heteroatom-hydrogen insertion reactions, cyclopropanation, ylide formation, Wolff rearrangement, and cycloaddition reactions. PCDCs can be easily prepared from readily accessible precursors by a variety of different methods, such as diazotization, Bamford-Stevens-type elimination, and diazo transfer reactions. This evidence along with their relative stability and manageability make them appealing tools in organic synthesis. This Review aims to demonstrate the ongoing utility of PCDCs in the modern preparation of different classes of phosphorus-containing compounds, phosphonates, in particular. Furthermore, to address the lack of precedent collective papers, this Review also summarizes the methods for PCDCs preparation.

Diazo compounds for the bioreversible esterification of proteins† †Electronic supplementary information (ESI) available: Experimental procedures, analytical data, and spectral data for novel compounds. See DOI: 10.1039/c4sc01768d Click here for additional data file.

PubMed Central

McGrath, Nicholas A.; Andersen, Kristen A.; Davis, Amy K. F.; Lomax, Jo E.

2015-01-01

A diazo compound is shown to convert carboxylic acids to esters efficiently in an aqueous environment. The basicity of the diazo compound is critical: low basicity does not lead to a reaction but high basicity leads to hydrolysis. This reactivity extends to carboxylic acid groups in a protein. The ensuing esters are hydrolyzed by human cellular esterases to regenerate protein carboxyl groups. This new mode of chemical modification could enable the key advantages of prodrugs to be translated from small-molecules to proteins. PMID:25544883

Polar and low polar solvents media effect on dipole moments of some diazo Sudan dyes

NASA Astrophysics Data System (ADS)

Zakerhamidi, M. S.; Golghasemi Sorkhabi, Sh.; Shamkhali, A. N.

2014-06-01

Absorption and fluorescence spectra of three Sudan dyes (SudanIII, SudanIV and Sudan black B) were recorded in various solvents with different polarity in the range of 300-800 nm, at room temperature. The solvatochromic method was used to investigate dipole moments of these dyes in ground and excited states, in different media. The solvatochromic behavior of these substances and their solvent-solute interactions were analyzed via solvent polarity parameters. Obtained results express the effects of solvation on tautomerism and molecular configuration (geometry) of Sudan dyes in solvent media with different polarity. Furthermore, analyze of solvent-solute interactions and value of ground and excited states dipole moments suggests different forms of resonance structures for Sudan dyes in polar and low-polar solvents.

Synthesis and evaluation of changes induced by solvent and substituent in electronic absorption spectra of some azo disperse dyes

NASA Astrophysics Data System (ADS)

Mohammadi, Asadollah; Yazdanbakhsh, Mohammad Reza; Farahnak, Lahya

2012-04-01

Five azo disperse dyes were prepared by diazotizing 4'-aminoacetophenone and p-anisidine and coupling with varies N-alkylated aromatic amines. Characterization of the dyes was carried out by using UV-vis, FTIR and 1H NMR spectroscopic techniques. The electronic absorption spectra of dyes are determined at room temperature in fifteen solvents with different polarities. The solvent dependent maximum absorption band shifts, were investigated using dielectric constant (ɛ), refractive index (n) and Kamlet-Taft polarity parameters (hydrogen bond donating ability (α), hydrogen bond accepting ability (β) and dipolarity/polarizability polarity scale (π*)). Acceptable agreement was found between the maximum absorption band of dyes and solvent polarity parameters especially with π*. The effect of substituents of coupler and/or diazo component on the color of dyes was investigated. The effects of acid and base on the visible absorption maxima of the dyes are also reported.

Synthesis, structural characterization and tautomeric properties of some novel bis-azo dyes derived from 5-arylidene-2,4-thiazolidinone

NASA Astrophysics Data System (ADS)

Mohammadi, Asadollah; Safarnejad, Mastaneh

Nine new bis-azo dyes derived from 5-arylidene-2,4-thiazolidinone have been synthesized in two steps using Knoevenagel condensation and diazotization-coupling reaction. The structures of the compounds were confirmed by UV-vis, IR, 1H NMR and 13C NMR spectroscopic techniques. The spectral characterizations demonstrate that there is an equilibrium between the azo (T1) and hydrazine (T2 and T3) tautomers for all prepared dyes in solutions. In addition, the solvatochromic behavior of the prepared dyes was evaluated using polarity/polarizability parameter (π*) in various solvents. The UV-vis absorption spectra of dyes show a bathochromic shift with increasing polarity and base strength of the solvents. Finally, the effects of acid and base on the UV-vis absorption spectra of the dyes with different substituent in diazo component are reported.

Palladium-catalyzed C-H functionalization of acyldiazomethane and tandem cross-coupling reactions.

PubMed

Ye, Fei; Qu, Shuanglin; Zhou, Lei; Peng, Cheng; Wang, Chengpeng; Cheng, Jiajia; Hossain, Mohammad Lokman; Liu, Yizhou; Zhang, Yan; Wang, Zhi-Xiang; Wang, Jianbo

2015-04-08

Palladium-catalyzed C-H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consistent with the experimental results, the density functional theory (DFT) calculation indicates that the formation of Pd-carbene species in the catalytic cycle through dinitrogen extrusion from the palladium ethyl diazoacetate (Pd-EDA) complex is less favorable. The reaction instead proceeds through Ag2CO3 assisted deprotonation and subsequently reductive elimination to afford the products with diazo functionality remained. This C-H functionalization transformation can be further combined with the recently evolved palladium-catalyzed cross-coupling reaction of diazo compounds with aryl iodides to develop a tandem coupling process for the synthesis of α,α-diaryl esters. DFT calculation supports the involvement of Pd-carbene as reactive intermediate in the catalytic cycle, which goes through facile carbene migratory insertion with a low energy barrier (3.8 kcal/mol).

Diazo dye Congo Red degradation using a Boron-doped diamond anode: An experimental study on the effect of supporting electrolytes.

PubMed

Jalife-Jacobo, H; Feria-Reyes, R; Serrano-Torres, O; Gutiérrez-Granados, S; Peralta-Hernández, Juan M

2016-12-05

Diazo dye Congo Red (CR) solutions at 100mg/L, were degraded using different supporting electrolytes in an electrochemical advanced oxidation process (EAOPs), like the anodic oxidation (AOx/BDD). All experiments were carried out in a 3L flow reactor with a Boron-doped diamond (BDD) anode and stainless steel cathode (AISI 304), at 7.5, 15, 30 and 50mA/cm(2) current densities (j). Furthermore, each experiment was carried out under a flow rate of 7L/min. Additionally, HClO4, NaCl, Na2SO4, and H2SO4 were tested as supporting electrolytes at a 50mM concentration. The degradation process was at all times considerably faster in NaCl medium. Solutions containing SO4(2-) or ClO4(-) ions were less prompted to degradation due to the low oxidation power of these species into the bulk. Dissolved organic carbon (DOC) analysis, was carried out to evaluate the mineralization of CR. The degradation of CR, was evaluated with the HPLC analysis of the treated solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Multifunctional PMMA@Fe3O4@DR Magnetic Materials for Efficient Adsorption of Dyes

PubMed Central

Yu, Bing; He, Liang; Wang, Yifan

2017-01-01

Magnetic porous microspheres are widely used in modern wastewater treatment technology due to their simple and quick dye adsorption and separation functions. In this article, we prepared porous polymethylmethacrylate (PMMA) microspheres by the seed-swelling method, followed by in situ formation of iron oxide (Fe3O4) nanoparticles within the pore. Then, we used diazo-resin (DR) to encapsulate the porous magnetic microspheres and achieve PMMA@Fe3O4@DR magnetic material. We studied the different properties of magnetic microspheres by different dye adsorption experiments before and after the encapsulation and demonstrated that the PMMA@Fe3O4@DR microspheres can be successfully used as a reusable absorbent for fast and easy removal of anionic and aromatic dyes from wastewater and can maintain excellent magnetic and adsorption properties in harsh environments. PMID:29077025

Flow chemistry as a discovery tool to access sp2-sp3 cross-coupling reactions via diazo compounds.

PubMed

Tran, Duc N; Battilocchio, Claudio; Lou, Shing-Bong; Hawkins, Joel M; Ley, Steven V

2015-02-01

The work takes advantage of an important feature of flow chemistry, whereby the generation of a transient species (or reactive intermediate) can be followed by a transfer step into another chemical environment, before the intermediate is reacted with a coupling partner. This concept is successfully applied to achieve a room temperature sp 2 -sp 3 cross coupling of boronic acids with diazo compounds, these latter species being generated from hydrazones under flow conditions using MnO 2 as the oxidant.

Direct identification of early synthetic dyes: FT-Raman study of the illustrated broadside prints of José Gaudalupe Posada (1852-1913)

NASA Astrophysics Data System (ADS)

Casadio, F.; Mauck, K.; Chefitz, M.; Freeman, R.

2010-09-01

Fourier Transform (FT)-Raman spectroscopy was used for the non-invasive, direct identification of colorants used to dye historical printed papers, overcoming obstacles such as low concentration of the dye, faded colors and fluorescence interference of the aged paper substrate. Based on a newly created FT-Raman reference database of 20 widely used dyes in the 19th century paper industry, the detectability of these dyes on aged biomaterials was determined by studying dyed paper samples from contemporary dye manuals, and identifying diagnostic peaks detectable on those substrates. Lastly, the method was applied to analyze the colorants used to dye the papers of a group of prints illustrated by the influential Mexico City artist José Guadalupe Posada, active 1876-1913. Unambiguous identification of the synthetic organic colorants Malachite Green (a triarylmethane dye), Orange II and Metanil Yellow (two acid monoazo dyes), Cotton Scarlet (an acid diazo dye), Phloxine (a xanthene dye) and Victoria Blue (a triarylmethane dye) in several of Posada’s prints challenged previous art-historical assumptions that these artworks were colored with natural dyes. The acquired knowledge has important conservation implications given that aniline dyes are sensitive to light and to aqueous treatments otherwise commonly carried out on works of art on paper.

Response surface methodological approach for the decolorization of simulated dye effluent using Aspergillus fumigatus fresenius.

PubMed

Sharma, Praveen; Singh, Lakhvinder; Dilbaghi, Neeraj

2009-01-30

The aim of our research was to study, effect of temperature, pH and initial dye concentration on decolorization of diazo dye Acid Red 151 (AR 151) from simulated dye solution using a fungal isolate Aspergillus fumigatus fresenius have been investigated. The central composite design matrix and response surface methodology (RSM) have been applied to design the experiments to evaluate the interactive effects of three most important operating variables: temperature (25-35 degrees C), pH (4.0-7.0), and initial dye concentration (100-200 mg/L) on the biodegradation of AR 151. The total 20 experiments were conducted in the present study towards the construction of a quadratic model. Very high regression coefficient between the variables and the response (R(2)=0.9934) indicated excellent evaluation of experimental data by second-order polynomial regression model. The RSM indicated that initial dye concentration of 150 mg/L, pH 5.5 and a temperature of 30 degrees C were optimal for maximum % decolorization of AR 151 in simulated dye solution, and 84.8% decolorization of AR 151 was observed at optimum growth conditions.

Exploring the potential of anaerobic sulfate reduction process in treating sulfonated diazo dye: Microbial community analysis using bar-coded pyrosequencing.

PubMed

Rasool, Kashif; Shahzad, Asif; Lee, Dae Sung

2016-11-15

Anaerobic decolorization and biotransformation of azo dye was investigated in a sulfate-reducing environment. Batch reactor studies were performed with mixed cultures of anaerobic sulfate-reducing bacteria (SRBs) enriched from anaerobic digester sludge. Complete sulfate and color removal were achieved in batch experiments with different initial dye concentrations (50-2500mg/L) and 1000mg/L of sulfate. Induction of various oxidoreductive enzyme activities such as phenol oxidase, veratryl alcohol oxidase, lignin peroxidase, and azo reductase was studied to understand their involvement in dye metabolism under anoxic environment. The degradation of Cotton Red B was confirmed using high-performance liquid chromatography and gas chromatography-mass spectroscopy. Sulfidogenic sludge demonstrated excellent dye degradation and mineralization ability, producing aniline and 1,4-diamino benzene as metabolites. A barcoded 16S rRNA gene-pyrosequencing approach was used to assess the bacterial diversity in the sludge culture and a phylogenetic tree was constructed for sulfate-reducing bacteria. Copyright © 2016 Elsevier B.V. All rights reserved.

On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation

PubMed Central

Mereshchenko, Andrey S; Ivanov, Alexey V; Baranovskii, Viktor I; Rodina, Ludmila L

2015-01-01

Summary The 1,3-dipolar cycloaddition of acyclic 2-diazo-1,3-dicarbonyl compounds (DDC) and thioketones preferably occurs with Z,E-conformers and leads to the formation of transient thiocarbonyl ylides in two stages. The thermodynamically favorable further transformation of C=S ylides bearing at least one acyl group is identified as the 1,5-electrocyclization into 1,3-oxathioles. However, in the case of diazomalonates, the dominating process is 1,3-cyclization into thiiranes followed by their spontaneous desulfurization yielding the corresponding alkenes. Finally, carbocyclic diazodiketones are much less reactive under similar conditions due to the locked cyclic structure and are unfavorable for the 1,3-dipolar cycloaddition due to the Z,Z-conformation of the diazo molecule. This structure results in high, positive values of the Gibbs free energy change for the first stage of the cycloaddition process. PMID:25977725

Enhancement and evaluation of Skylab photography for potential land use inventories, part 1. [New York

NASA Technical Reports Server (NTRS)

Hardy, E. E. (Principal Investigator); Skaley, J. E.; Dawson, C. P.; Weiner, G. D.; Phillips, E. S.; Fisher, R. A.

1975-01-01

The author has identified the following significant results. Three sites were evaluated for land use inventory: Finger Lakes - Tompkins County, Lower Hudson Valley - Newburgh, and Suffolk County - Long Island. Special photo enhancement processes were developed to standardize the density range and contrast among S190A negatives. Enhanced black and white enlargements were converted to color by contact printing onto diazo film. A color prediction model related the density values on each spectral band for each category of land use to the spectral properties of the various diazo dyes. The S190A multispectral system proved to be almost as effective as the S190B high resolution camera for inventorying land use. Aggregate error for Level 1 averaged about 12% while Level 2 aggregate error averaged about 25%. The S190A system proved to be much superior to LANDSAT in inventorying land use, primarily because of increased resolution.

Degradation pathway of the naphthalene azo dye intermediate 1-diazo-2- naphthol-4-sulfonic acid using Fenton's reagent.

PubMed

Zhu, Nanwen; Gu, Lin; Yuan, Haiping; Lou, Ziyang; Wang, Liang; Zhang, Xin

2012-08-01

Degradation of naphthalene dye intermediate 1-diazo-2- naphthol-4-sulfonic acid (1,2,4-Acid) by Fenton process has been studied in depth for the purpose of learning more about the reactions involved in the oxidation of 1,2,4-Acid. During 1,2,4-Acid oxidation, the solution color initially takes on a dark red, then to dark black associated with the formation of quinodial-type structures, and then goes to dark brown and gradually disappears, indicating a fast degradation of azo group. The observed color changes of the solution are a result of main reaction intermediates, which can be an indicator of the level of oxidization reached. Nevertheless, complete TOC removal is not accomplished, in accordance with the presence of resistant carboxylic acids at the end of the reaction. The intermediates generated along the reaction time have been identified and quantified. UPLC-(ESI)-TOF-HRMS analysis allows the detection of 19 aromatic compounds of different size and complexity. Some of them share the same accurate mass but appear at different retention time, evidencing their different molecular structures. Heteroatom oxidation products like SO(4)(2-) have also been quantified and explanations of their release are proposed. Short-chain carboxylic acids are detected at long reaction time, as a previous step to complete the process of dye mineralization. Finally, considering all the findings of the present study and previous related works, the evolution from the original 1,2,4-Acid to the final products is proposed in a general reaction scheme. Copyright © 2012 Elsevier Ltd. All rights reserved.

Diastereoselective Radical‐Type Cyclopropanation of Electron‐Deficient Alkenes Mediated by the Highly Active Cobalt(II) Tetramethyltetraaza[14]annulene Catalyst

PubMed Central

Chirila, Andrei; Gopal Das, Braja; Paul, Nanda D.

2017-01-01

Abstract A new protocol for the catalytic synthesis of cyclopropanes using electron‐deficient alkenes is presented, which is catalysed by a series of affordable, easy to synthesise and highly active substituted cobalt(II) tetraaza[14]annulenes. These catalysts are compatible with the use of sodium tosylhydrazone salts as precursors to diazo compounds in one‐pot catalytic transformations to afford the desired cyclopropanes in almost quantitative yields. The reaction takes advantage of the metalloradical character of the Co complexes to activate the diazo compounds. The reaction is practical and fast, and proceeds from readily available starting materials. It does not require the slow addition of diazo reagents or tosylhydrazone salts or heating and tolerates many solvents, which include protic ones such as MeOH. The CoII complexes derived from the tetramethyltetraaza[14]annulene ligand are easier to prepare than cobalt(II) porphyrins and present a similar catalytic carbene radical reactivity but are more active. The reaction proceeds at 20 °C in a matter of minutes and even at −78 °C in a few hours. The catalytic system is robust and can operate with either the alkene or the diazo reagent as the limiting reagent, which inhibits the dimerisation of diazo compounds totally. The protocol has been applied to synthesise a variety of substituted cyclopropanes. High yields and selectivities were achieved for various substrates with an intrinsic preference for trans cyclopropanes. PMID:28529668

A low-cost wheat bran medium for biodegradation of the benzidine-based carcinogenic dye Trypan Blue using a microbial consortium.

PubMed

Lade, Harshad; Kadam, Avinash; Paul, Diby; Govindwar, Sanjay

2015-03-25

Environmental release of benzidine-based dyes is a matter of health concern. Here, a microbial consortium was enriched from textile dye contaminated soils and investigated for biodegradation of the carcinogenic benzidine-based dye Trypan Blue using wheat bran (WB) as growth medium. The PCR-DGGE analysis of enriched microbial consortium revealed the presence of 15 different bacteria. Decolorization studies suggested that the microbial consortium has high metabolic activity towards Trypan Blue as complete removal of 50 mg∙L-1 dye was observed within 24 h at 30 ± 0.2 °C and pH 7. Significant reduction in TOC (64%) and COD (88%) of dye decolorized broths confirmed mineralization. Induction in azoreductase (500%), NADH-DCIP reductase (264%) and laccase (275%) proved enzymatic decolorization of dye. HPLC analysis of dye decolorized products showed the formation of six metabolites while the FTIR spectrum indicated removal of diazo bonds at 1612.30 and 1581.34 cm-1. The proposed dye degradation pathway based on GC-MS and enzyme analysis suggested the formation of two low molecular weight intermediates. Phytotoxicity and acute toxicity studies revealed the less toxic nature of the dye degradation products. These results provide experimental evidence for the utilization of agricultural waste as a novel low-cost growth medium for biodegradation of benzidine-based dyes, and suggested the potential of the microbial consortium in detoxification.

A Low-Cost Wheat Bran Medium for Biodegradation of the Benzidine-Based Carcinogenic Dye Trypan Blue Using a Microbial Consortium

PubMed Central

Lade, Harshad; Kadam, Avinash; Paul, Diby; Govindwar, Sanjay

2015-01-01

Environmental release of benzidine-based dyes is a matter of health concern. Here, a microbial consortium was enriched from textile dye contaminated soils and investigated for biodegradation of the carcinogenic benzidine-based dye Trypan Blue using wheat bran (WB) as growth medium. The PCR-DGGE analysis of enriched microbial consortium revealed the presence of 15 different bacteria. Decolorization studies suggested that the microbial consortium has high metabolic activity towards Trypan Blue as complete removal of 50 mg∙L−1 dye was observed within 24 h at 30 ± 0.2 °C and pH 7. Significant reduction in TOC (64%) and COD (88%) of dye decolorized broths confirmed mineralization. Induction in azoreductase (500%), NADH-DCIP reductase (264%) and laccase (275%) proved enzymatic decolorization of dye. HPLC analysis of dye decolorized products showed the formation of six metabolites while the FTIR spectrum indicated removal of diazo bonds at 1612.30 and 1581.34 cm−1. The proposed dye degradation pathway based on GC-MS and enzyme analysis suggested the formation of two low molecular weight intermediates. Phytotoxicity and acute toxicity studies revealed the less toxic nature of the dye degradation products. These results provide experimental evidence for the utilization of agricultural waste as a novel low-cost growth medium for biodegradation of benzidine-based dyes, and suggested the potential of the microbial consortium in detoxification. PMID:25815522

Flow chemistry as a discovery tool to access sp2–sp3 cross-coupling reactions via diazo compounds† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03072a Click here for additional data file.

PubMed Central

Tran, Duc N.; Battilocchio, Claudio; Lou, Shing-Bong; Hawkins, Joel M.

2015-01-01

The work takes advantage of an important feature of flow chemistry, whereby the generation of a transient species (or reactive intermediate) can be followed by a transfer step into another chemical environment, before the intermediate is reacted with a coupling partner. This concept is successfully applied to achieve a room temperature sp2–sp3 cross coupling of boronic acids with diazo compounds, these latter species being generated from hydrazones under flow conditions using MnO2 as the oxidant. PMID:29560199

Chemical Posttranslational Modification with Designed Rhodium(II) Catalysts.

PubMed

Martin, S C; Minus, M B; Ball, Z T

2016-01-01

Natural enzymes use molecular recognition to perform exquisitely selective transformations on nucleic acids, proteins, and natural products. Rhodium(II) catalysts mimic this selectivity, using molecular recognition to allow selective modification of proteins with a variety of functionalized diazo reagents. The rhodium catalysts and the diazo reactivity have been successfully applied to a variety of protein folds, the chemistry succeeds in complex environments such as cell lysate, and a simple protein blot method accurately assesses modification efficiency. The studies with rhodium catalysts provide a new tool to study and probe protein-binding events, as well as a new synthetic approach to protein conjugates for medical, biochemical, or materials applications. © 2016 Elsevier Inc. All rights reserved.

Optical sensing elements for nitrogen dioxide (NO.sub.2) gas detection, a sol-gel method for making the sensing elements and fiber optic sensors incorporating nitrogen dioxide gas optical sensing elements

DOEpatents

Mechery, Shelly John [Mississippi State, MS; Singh, Jagdish P [Starkville, MS

2007-07-03

A sensing element, a method of making a sensing element, and a fiber optic sensor incorporating the sensing element are described. The sensor can be used for the quantitative detection of NO.sub.2 in a mixture of gases. The sensing element can be made by incorporating a diazotizing reagent which reacts with nitrous ions to produce a diazo compound and a coupling reagent which couples with the diazo compound to produce an azo dye into a sol and allowing the sol to form an optically transparent gel. The sensing element changes color in the presence of NO.sub.2 gas. The temporal response of the absorption spectrum at various NO.sub.2 concentrations has also been recorded and analyzed. Sensors having different design configurations are described. The sensing element can detect NO.sub.2 gas at levels of parts per billion.

Synchronously Pumped Optical Parametric Oscillator with Intracavity Difference Frequency Mixing

DTIC Science & Technology

1998-06-29

Phys. B, vol. 63, no. 5, pp. 437-441, 1996. [11] T. Töpfer, K. P. Petrov, Y. Mine, L. E. Myers, and R. W. Wallace , "Room- temperature midinfrared...generation in diazo-dye-substitured polymer channel waveguides," IEEE J. of Quant. Electron., vol. 33, no. 3, pp. 349-357, 1997. [56] A. Szilagyi ...periodically poled lithium- niobate," Opt. Lett, vol. 23, no. 9, pp. 664-666, 1998. [119] W. R. Bosenberg, J. I. Alexander, L. E. Myers, and R. W. Wallace

Diazo Reagents with Small Steric Footprints for Simultaneous Arming/SAR Studies of Alcohol-Containing Natural Products via O–H Insertion

PubMed Central

Chamni, Supakarn; He, Qing-Li; Dang, Yongjun; Bhat, Shridhar; Liu, Jun O.; Romo, Daniel

2011-01-01

Natural products are essential tools for basic cellular studies leading to the identification of medically relevant protein targets and the discovery of potential therapeutic leads. The development of methods that enable mild and selective derivatization of natural products continues to be of significant interest for mining their information-rich content. Herein, we describe novel diazo reagents for simultaneous arming and structure-activity relationship (SAR) studies of alcohol-containing natural products with a small steric footprint, namely an α-trifluoroethyl (HTFB) substituted reagent. The Rh(II)-catalyzed O–H insertion reaction of several natural products, including the potent translation inhibitor lactimidomycin, was investigated and useful reactivity and both chemo- and site (chemosite) selectivities were observed. Differential binding to the known protein targets of both FK506 and fumagillol was demonstrated, validating the advantage of the smaller steric footprint of trifluoroethyl derivatives. A p-azidophenyl diazo reagent is also described that will prove useful for photoaffinity labeling of low affinity small molecule protein receptors. PMID:21894934

Comparative Studies on Dyeability with Direct, Acid and Reactive Dyes after Chemical Modification of Jute with Mixed Amino Acids Obtained from Extract of Waste Soya Bean Seeds

NASA Astrophysics Data System (ADS)

Bhaumik, Nilendu Sekhar; Konar, Adwaita; Roy, Alok Nath; Samanta, Ashis Kumar

2017-12-01

Jute fabric was treated with mixed natural amino acids obtained from waste soya bean seed extract for chemical modification of jute for its cataionization and to enhance its dyeability with anionic dyes (like direct, reactive and acid dye) as well enabling soya modified jute for salt free dyeing with anionic reactive dyes maintaining its eco-friendliness. Colour interaction parameters including surface colour strength were assessed and compared for both bleached and soya-modified jute fabric for reactive dyeing and compared with direct and acid dye. Improvement in K/S value (surface colour strength) was observed for soya-modified jute even in absence of salt applied in dye bath for reactive dyes as well as for direct and acid dyes. In addition, reactive dye also shows good dyeability even in acid bath in salt free conditions. Colour fastness to wash was evaluated for bleached and soya-modified jute fabric after dyeing with direct, acid and reactive dyes are reported. Treatment of jute with soya-extracted mixed natural amino acids showed anchoring of some amino/aldemine groups on jute cellulosic polymer evidenced from Fourier Transform Infra-Red (FTIR) Spectroscopy. This amino or aldemine group incorporation in bleached jute causes its cationization and hence when dyed in acid bath for reactive dye (instead of conventional alkali bath) showed dye uptake for reactive dyes. Study of surface morphology by Scanning Electron Microscopy (SEM) of said soya-modified jute as compared to bleached jute was studied and reported.

Bacterial decolorization of textile dyes is an extracellular process requiring a multicomponent electron transfer pathway

PubMed Central

Brigé, Ann; Motte, Bart; Borloo, Jimmy; Buysschaert, Géraldine; Devreese, Bart; Van Beeumen, Jozef J.

2008-01-01

Summary Many studies have reported microorganisms as efficient biocatalysts for colour removal of dye‐containing industrial wastewaters. We present the first comprehensive study to identify all molecular components involved in decolorization by bacterial cells. Mutants from the model organism Shewanella oneidensis MR‐1, generated by random transposon and targeted insertional mutagenesis, were screened for defects in decolorization of an oxazine and diazo dye. We demonstrate that decolorization is an extracellular reduction process requiring a multicomponent electron transfer pathway that consists of cytoplasmic membrane, periplasmic and outer membrane components. The presence of melanin, a redox‐active molecule excreted by S. oneidensis, was shown to enhance the dye reduction rates. Menaquinones and the cytochrome CymA are the crucial cytoplasmic membrane components of the pathway, which then branches off via a network of periplasmic cytochromes to three outer membrane cytochromes. The key proteins of this network are MtrA and OmcB in the periplasm and outer membrane respectively. A model of the complete dye reduction pathway is proposed in which the dye molecules are reduced by the outer membrane cytochromes either directly or indirectly via melanin. PMID:21261820

Nucleophilic Addition of Reactive Dyes on Amidoximated Acrylic Fabrics

PubMed Central

El-Shishtawy, Reda M.; El-Zawahry, Manal M.; Abdelghaffar, Fatma; Ahmed, Nahed S. E.

2014-01-01

Seven reactive dyes judiciously selected based on chemical structures and fixation mechanisms were applied at 2% owf of shade on amidoximated acrylic fabrics. Amidoximated acrylic fabric has been obtained by a viable amidoximation process. The dyeability of these fabrics was evaluated with respect to the dye exhaustion, fixation, and colour strength under different conditions of temperature and dyeing time. Nucleophilic addition type reactive dyes show higher colour data compared to nucleophilic substitution ones. FTIR studies further implicate the binding of reactive dyes on these fabrics. A tentative mechanism is proposed to rationalize the high fixation yield obtained using nucleophilic addition type reactive dyes. Also, the levelling and fastness properties were evaluated for all dyes used. Excellent to good fastness and levelling properties were obtained for all samples irrespective of the dye used. The result of investigation offers a new method for a viable reactive dyeing of amidoximated acrylic fabrics. PMID:25258720

Asthma, rhinitis, and dermatitis in workers exposed to reactive dyes.

PubMed Central

Nilsson, R; Nordlinder, R; Wass, U; Meding, B; Belin, L

1993-01-01

A survey was conducted at 15 textile plants with dyehouses in western Sweden. Employees with a history of work related rhinitis, asthma, or skin symptoms were offered a clinical and immunological investigation including skin prick tests, skin patch tests, and radioallergosorbent tests (RASTs) to detect specific allergy to reactive dyes. Among the 1142 employees, 162 were exposed to reactive dyes and 10 of these (6%) reported work related respiratory or nasal symptoms. An allergy to reactive dyes could be confirmed in five (3%, 95% confidence interval 1-7%). All but one had been exposed to reactive dyes for one year or less before the onset of symptoms. Positive RASTs could be detected in four of the five patients. All of the RAST positive patients were positive to remazol black B, but six out of eight additional remazol dyes also elicited positive results. RAST and RAST inhibition showed a cross reactivity between some of the dyes. Seven persons with work related dermatitis and three with urticaria or Quincke oedema were found. In one patient contact dermatitis to a monoazo dye was shown, but no positive patch test reactions to reactive dyes. IgE-mediated allergy to reactive dyes seems to be an important cause of respiratory and nasal symptoms among dyehouse employees exposed to dust from reactive dyes. PMID:8431393

Enzymatic decolourisation of Methyl Orange and Bismarck Brown using crude peroxidase from Armoracia rusticana

NASA Astrophysics Data System (ADS)

Ambatkar, Mugdha; Mukundan, Usha

2015-12-01

The decolourisation of Methyl Orange (MO) and Bismarck Brown (BB) by crude peroxidase from Armoracia rusticana (Horseradish) was studied by varying different reaction parameters. The pH of the reaction mixture, initial dye concentration, amount of enzyme and hydrogen peroxide concentration were optimised for ambient temperatures (30 ± 2 °C). The optimum pH for decolourisation was 4.0 (72.95 %) and 3.0 (79.24 %) for MO and BB, respectively. Also it was found that the Chemical Oxygen Demand of the enzyme-treated sample was significantly lower than that of the untreated controls for both dyes. The addition of a complex iron salt like Ferric EDTA was found to enhance the decolourisation of both dyes at pH 6.0, showing an increase of 8.69 % and 14.17 % in the decolourisation of MO and of BB, respectively. The present study explores the potential of crude peroxidase from horseradish to decolourise representative monoazo and diazo dyes, MO and BB, respectively. An attempt has been made to utilise a crude enzyme with appreciable activity obtained after minimal processing for the decolourisation of the aforesaid dyes. The findings of this study would find application in the enzymatic treatment of wastewater containing azo dyes.

Rapid and direct spectrophotometric method for kinetics studies and routine assay of peroxidase based on aniline diazo substrates.

PubMed

Mirazizi, Fatemeh; Bahrami, Azita; Haghbeen, Kamahldin; Shahbani Zahiri, Hossein; Bakavoli, Mehdi; Legge, Raymond L

2016-12-01

Peroxidases are ubiquitous enzymes that play an important role in living organisms. Current spectrophotometrically based peroxidase assay methods are based on the production of chromophoric substances at the end of the enzymatic reaction. The ambiguity regarding the formation and identity of the final chromophoric product and its possible reactions with other molecules have raised concerns about the accuracy of these methods. This can be of serious concern in inhibition studies. A novel spectrophotometric assay for peroxidase, based on direct measurement of a soluble aniline diazo substrate, is introduced. In addition to the routine assays, this method can be used in comprehensive kinetics studies. 4-[(4-Sulfophenyl)azo]aniline (λmax = 390 nm, ɛ = 32 880 M(-1) cm(-1) at pH 4.5 to 9) was introduced for routine assay of peroxidase. This compound is commercially available and is indexed as a food dye. Using this method, a detection limit of 0.05 nmol mL(-1) was achieved for peroxidase.

Allergic contact dermatitis associated with reactive dyes in a dark garment: a case report.

PubMed

Moreau, Linda; Goossens, An

2005-09-01

In this study, we present a case of a patient who has not been occupationally exposed to reactive dyes, but did present with a dermatitis from wearing a dark cotton garment. The patient experienced reactivation of his dermatitis when rewearing a new unwashed dark T-shirt made of 100% cotton (in fact, the patient reported that it had to be washed at least 3 times before the skin reaction disappeared). He presented positive patch tests to 6 reactive dyes from Chemotechnique textile series. The clothing could not be proved as the true cause of the dermatitis, but resolution occurred upon removal of the suspected garment. This suggests that contact allergy to the reactive dyes (he did not react to any other dyes and his garment was a natural fabric) was likely responsible. With this report, we would like to emphasize that reactive dyes, as a class, should be considered as potential allergens, both occupationally and from non-occupational exposure such as garments. If garments containing reactive dyes are not properly rinsed in the manufacturing process, we believe that excess of dye can be retained that may cause allergic contact dermatitis (ACD). As the reactive dyes and their hydrolysis products are very water-soluble, they can be easily washed off to prevent ACD.

Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters.

PubMed

Thomas, Bryce N; Moon, Patrick J; Yin, Shengkang; Brown, Alex; Lundgren, Rylan J

2018-01-07

A well-defined Ir-allyl complex catalyzes the Z -selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E -products typically observed in metal-mediated coupling reactions to enable the synthesis of Z , E -dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir-carbene and Ir-allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E-H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt 3 .

Cold Pad-Batch dyeing method for cotton fabric dyeing with reactive dyes using ultrasonic energy.

PubMed

Khatri, Zeeshan; Memon, Muhammad Hanif; Khatri, Awais; Tanwari, Anwaruddin

2011-11-01

Reactive dyes are vastly used in dyeing and printing of cotton fibre. These dyes have a distinctive reactive nature due to active groups which form covalent bonds with -OH groups of cotton through substitution and/or addition mechanism. Among many methods used for dyeing cotton with reactive dyes, the Cold Pad Batch (CPB) method is relatively more environment friendly due to high dye fixation and non requirement of thermal energy. The dyed fabric production rate is low due to requirement of at least twelve hours batching time for dye fixation. The proposed CPB method for dyeing cotton involves ultrasonic energy resulting into a one third decrease in batching time. The dyeing of cotton fibre was carried out with CI reactive red 195 and CI reactive black 5 by conventional and ultrasonic (US) method. The study showed that the use of ultrasonic energy not only shortens the batching time but the alkalis concentrations can considerably be reduced. In this case, the colour strength (K/S) and dye fixation (%F) also enhances without any adverse effect on colour fastness of the dyed fabric. The appearance of dyed fibre surface using scanning electron microscope (SEM) showed relative straightening of fibre convolutions and significant swelling of the fibre upon ultrasonic application. The total colour difference values ΔE (CMC) for the proposed method, were found within close proximity to the conventionally dyed sample. Copyright © 2011 Elsevier B.V. All rights reserved.

Discovery of a diazo-forming enzyme in cremeomycin biosynthesis.

PubMed

Waldman, Abraham J; Balskus, Emily P

2018-05-17

The molecular architectures and potent bioactivities of diazo-containing natural products have attracted the interest of synthetic and biological chemists. Despite this attention, the biosynthetic enzymes involved in diazo group construction have not been identified. Here, we show the ATP-dependent enzyme CreM installs the diazo group in cremeomycin via late-stage N-N bond formation using nitrite. This finding should inspire efforts to use diazo-forming enzymes in biocatalysis and synthetic biology and enable genome-based discovery of new diazo-containing metabolites.

Performance evaluation of two Aspergillus spp. for the decolourization of reactive dyes by bioaccumulation and biosorption.

PubMed

Mathur, Megha; Gola, Deepak; Panja, Rupobrata; Malik, Anushree; Ahammad, Shaikh Ziauddin

2018-01-01

A biological method was adopted to decolourize textile dyes, which is an economic and eco-friendly technology for textile wastewater remediation. Two fungal strains, i.e. Aspergillus lentulus and Aspergillus fumigatus, were used to study the removal of low to high concentrations (25 to 2000 mg L -1 ) of reactive remazol red, reactive blue and reactive yellow dyes by biosorption and bioaccumulation. The biosorption was successful only at the lower concentrations. A. lentulus was capable of removing 67-85% of reactive dyes during bioaccumulation mode of treatment at 500 mg L -1 dye concentration with an increased biomass uptake capacity. To cope up with the high dye concentration of 2000 mg L -1 , a novel combined approach was successful in case of A. lentulus, where almost 76% removal of reactive remazol red dye was observed during bioaccumulation followed by biosorption. The scanning electron microscopy also showed the accumulation of dye on the surface of fungal mycelium. The results signify the application of such robust fungal strains for the removal of high concentration of dyes in the textile wastewaters.

Ultrasonic dyeing of cellulose nanofibers.

PubMed

Khatri, Muzamil; Ahmed, Farooq; Jatoi, Abdul Wahab; Mahar, Rasool Bux; Khatri, Zeeshan; Kim, Ick Soo

2016-07-01

Textile dyeing assisted by ultrasonic energy has attained a greater interest in recent years. We report ultrasonic dyeing of nanofibers for the very first time. We chose cellulose nanofibers and dyed with two reactive dyes, CI reactive black 5 and CI reactive red 195. The cellulose nanofibers were prepared by electrospinning of cellulose acetate (CA) followed by deacetylation. The FTIR results confirmed complete conversion of CA into cellulose nanofibers. Dyeing parameters optimized were dyeing temperature, dyeing time and dye concentrations for each class of the dye used. Results revealed that the ultrasonic dyeing produced higher color yield (K/S values) than the conventional dyeing. The color fastness test results depicted good dye fixation. SEM analysis evidenced that ultrasonic energy during dyeing do not affect surface morphology of nanofibers. The results conclude successful dyeing of cellulose nanofibers using ultrasonic energy with better color yield and color fastness results than conventional dyeing. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and evaluation of NLO properties of π-conjugated donor-acceptor systems bearing pyrrole and thiophene heterocycles

NASA Astrophysics Data System (ADS)

Castro, M. Cidália R.; Fonseca, A. Maurício C.; Belsley, M.; Raposo, M. Manuela M.

2011-05-01

Two series of novel push-pull heterocyclic azo dyes have been synthesized and characterized. The two series of compounds were based on different combinations of π-conjugated bridges (bithiophene and thienylpyrrole) which also act simultaneously as donor groups, together with diazo(benzo)thiazolyl as acceptor moieties. Their thermal stability and electrochemical behavior were characterized, while hyper-Rayleigh scattering (HRS) was employed to evaluate their second-order nonlinear optical properties. The results of these studies have been critically analyzed together with several thienylpyrrole azo dyes reported earlier from our laboratories in which the thienylpyrrole system was used as the donor group functionalized with aryl and (benzo)thiazolyldiazene as acceptor moiety. The measured molecular first hyperpolarizabilities and the observed linear optical and redox behavior showed strong variations in function of the heterocyclic spacers used (bithiophene or thienylpyrrole) and were also sensitive to the acceptor strength of the diazenehetero(aryl) moiety.

Time-dependent efficiency measurements of donor-acceptor, dye-sensitized polymer solar cells

NASA Astrophysics Data System (ADS)

Bandaccari, Kyle; Chesmore, Grace; Tajalli-Tehrani Valverde, Parisa; Bugaj, Mitchel; McNelis, Brian; Barber, Richard, Jr.

The fullerene/polymer active layer pairing of PCBM/P3HT has become the model system within the field of polymer solar cell research. A large body of work concerned with reporting improved efficiencies for this system exists, but truly quantitative studies of device lifetime and long-term degradation tendencies are much rarer. Here, we report the effects of two donor-acceptor diazo dye sensitizers on efficiency and lifetime upon addition into the PCBM/P3HT active layer at varied concentrations. The electrical and efficiency measurements were supplemented by time-dependent UV-visible spectroscopy studies and morphology investigations via atomic-force microscopy (AFM). This pairing with spectroscopy offers an internal check on the data as the rate of change in absorbance of the active layer correlates almost exactly to the rate of power conversion efficiency decrease. Additionally, AFM imaging reveals different morphology patterns when dye concentrations and functionalities change. Such observations suggest that such small-molecule sensitizers exert yet undetermined effects on the organization of components within the active layer at the molecular level.

Rh(II)-catalyzed reactions of differentially substituted bis(diazo) functionalities.

PubMed

Bonderoff, Sara A; Padwa, Albert

2013-08-16

The chemoselective reaction of donor/acceptor (D/A) and acceptor/acceptor (A/A) diazo moieties in the same molecule was examined using 3-diazo-1-(ethyl 2-diazomalonyl)indolin-2-one under rhodium(II) catalysis. The D/A diazo group undergoes selective cyclopropanation as well as XH-insertion, leaving behind the second diazo group for a further intramolecular dipolar cycloaddition reaction.

Batchwise dyeing of bamboo cellulose fabric with reactive dye using ultrasonic energy.

PubMed

Larik, Safdar Ali; Khatri, Awais; Ali, Shamshad; Kim, Seong Hun

2015-05-01

Bamboo is a regenerated cellulose fiber usually dyed with reactive dyes. This paper presents results of the batchwise dyeing of bamboo fabric with reactive dyes by ultrasonic (US) and conventional (CN) dyeing methods. The study was focused at comparing the two methods for dyeing results, chemicals, temperature and time, and effluent quality. Two widely used dyes, CI Reactive Black 5 (bis-sulphatoethylsulphone) and CI Reactive Red 147 (difluorochloropyrimidine) were used in the study. The US dyeing method produced around 5-6% higher color yield (K/S) in comparison to the CN dyeing method. A significant savings in terms of fixation temperature (10°C) and time (15 min), and amounts of salt (10 g/L) and alkali (0.5-1% on mass of fiber) was realized. Moreover, the dyeing effluent showed considerable reductions in the total dissolved solids content (minimum around 29%) and in the chemical oxygen demand (minimum around 13%) for the US dyebath in comparison to the CN dyebath. The analysis of colorfastness tests demonstrated similar results by US and CN dyeing methods. A microscopic examination on the field emission scanning electron microscope revealed that the US energy did not alter the surface morphology of the bamboo fibers. It was concluded that the US dyeing of bamboo fabric produces better dyeing results and is a more economical and environmentally sustainable method as compared to CN dyeing method. Copyright © 2014 Elsevier B.V. All rights reserved.

Homogenous and heterogenous advanced oxidation of two commercial reactive dyes.

PubMed

Balcioglu, I A; Arslan, I; Sacan, M T

2001-07-01

Two commercial reactive dyes, the azo dye Reactive Black 5 and the copper phythalocyanine dye Reactive Blue 21, have been treated at a concentration of 75 mg l(-1) by titanium dioxide mediated photocatalytic (TiO2/UV), dark and UV-light assisted Fenton (Fe2+/H2O2) and Fenton-like (Fe3+/H2O2) processes in acidic medium. For the treatment of Reactive Black 5, all investigated advanced oxidation processes were quite effective in terms of colour, COD as well as TOC removal. Moreover, the relative growth inhibition of the azo dye towards the marine algae Dunaliella tertiolecta that was initially 70%, did not exhibit an increase during the studied advanced oxidation reactions and complete detoxification at the end of the treatment period could be achieved for all investigated treatment processes. However, for Reactive Blue 21, abatement in COD and UV-VIS absorbance values was mainly due to the adsorption of the dye on the photocatalyst surface and/or the coagulative effect of Fe3+/Fe2+ ions. Although only a limited fraction of the copper phythalocyanine dye underwent oxidative degradation, 47% of the total copper in the dye was already released after 1 h photocatalytic treatment.

Pyridine group assisted addition of diazo-compounds to imines in the 3-CC reaction of 2-aminopyridines, aldehydes, and diazo-compounds.

PubMed

Gulevich, Anton V; Helan, Victoria; Wink, Donald J; Gevorgyan, Vladimir

2013-02-15

A novel three-component coupling (3-CC) reaction of 2-aminoazines, aromatic aldehydes, and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles as well as β-amino acid derivatives.

Synthesis of precursors to and spectroscopic characterization of highly unsaturated carbenes and diradicals and development and implementation of a web-based stereochemistry tutorial

NASA Astrophysics Data System (ADS)

Burrmann, Nicola Jean

A variety of substituted diynols, diynals, and diynones have been prepared en route to the synthesis of precursors to dialkynyl carbenes (R1--C≡C--C--C≡C--R 2). In light of the unique reactivity associated with these simple systems, several strategies were required to assemble the carbon backbones (Chapter I). Tosylhydrazone and trisylhydrazone precursors to 2-diazo-3-pentyne ( 1), 2-diazo-3-butyne (2), and Idiazo-2-butyne ( 3) were synthesized and then converted into their respective diazo compounds. Various attempts to study these diazo compounds using matrix isolation IR and EPR spectroscopy were made and proved to be unsuccessful. Computations were done to characterize the C5H6 potential energy surface, as well as to determine the IR vibrational frequencies of the isomers on this surface (Chapter 2). A web-based Stereochemistry Tutorial that details the core definitions and structural representations relevant to organic stereochemistry was designed and implemented into several introductory-level organic chemistry classes. This tutorial also allows for students to select their preferred structural representation and method for making stereochemical comparisons between molecules. The tutorial was evaluated, either qualitatively, quantitatively, or both, by students in three different introductory organic chemistry courses at the University of Wisconsin---Madison. The data show that students did use a variety of different methods for making stereochemical comparisons between molecules, and that prior exposure to lectures on stereochemistry by the course professor strongly influenced these choices. Furthermore, the level of improvement in stereochemical knowledge as a result of using only the tutorial was comparable to, or higher than, that achieved by students who were only exposed to lectures by the course professor, regardless of the method chosen for making stereochemical comparisons between molecules (Chapter 3)

Pyridine Group-Assisted Addition of Diazo-Compounds to Imines in the 3-CC Reaction of 2-Aminopyridines, Aldehydes, and Diazo-Compounds

PubMed Central

Gulevich, Anton V.; Helan, Victoria; Wink, Donald J.

2013-01-01

A novel three-component (3-CC) coupling reaction of 2-aminoazines, aromatic aldehydes and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles, as well as to β-amino acid derivatives. PMID:23373731

Direct C-H alkylation and indole formation of anilines with diazo compounds under rhodium catalysis.

PubMed

Mishra, Neeraj Kumar; Choi, Miji; Jo, Hyeim; Oh, Yongguk; Sharma, Satyasheel; Han, Sang Hoon; Jeong, Taejoo; Han, Sangil; Lee, Seok-Yong; Kim, In Su

2015-12-18

The rhodium(III)-catalyzed direct functionalization of aniline C-H bonds with α-diazo compounds is described. These transformations provide a facile construction of ortho-alkylated anilines with diazo malonates or highly substituted indoles with diazo acetoacetates.

Nanostructured ZnO-TiO2 thin film oxide as anode material in electrooxidation of organic pollutants. Application to the removal of dye Amido black 10B from water.

PubMed

El-Kacemi, Sana; Zazou, Hicham; Oturan, Nihal; Dietze, Matthias; Hamdani, Mohamed; Es-Souni, Mohammed; Oturan, Mehmet A

2017-01-01

Electrochemical oxidative degradation of diazo dye Amido black 10B (AB10B) as model pollutant in water has been studied using nanostructured ZnO-TiO 2 thin films deposited on graphite felt (GrF) substrate as anode. The influence of various operating parameters, namely the current intensity, the nature and concentration of catalyst, the nature of electrode materials (anode/cathode), and the adsorption of dye and ambient light were investigated. It was found that the oxidative degradation of AB10B followed pseudo first-order kinetics. The optimal operating conditions for the degradation of 0.12 mM (74 mg L -1 ) dye concentration and mineralization of its aqueous solution were determined as GrF-ZnO-TiO 2 thin film anode, 100 mA current intensity, and 0.1 mM Fe 2+ (catalyst) concentration. Under these operating conditions, discoloration of AB10B solution was reached at 60 min while 6 h treatment needed for a mineralization degree of 91 %. Therefore, this study confirmed that the electrochemical process is effective for the degradation of AB10B in water using nanostructured ZnO-TiO 2 thin film anodes.

Diazo Groups Endure Metabolism and Enable Chemoselectivity in Cellulo

PubMed Central

2015-01-01

We introduce a stabilized diazo group as a reporter for chemical biology. ManDiaz, which is a diazo derivative of N-acetylmannosamine, is found to endure cellular metabolism and label the surface of a mammalian cell. There its diazo group can undergo a 1,3-dipolar cycloaddition with a strained alkyne, providing a signal comparable to that from the azido congener, ManNAz. The chemoselectivity of diazo and alkynyl groups enables dual labeling of cells that is not possible with azido and alkynyl groups. Thus, the diazo group, which is approximately half the size of an azido group, provides unique opportunities for orthogonal labeling of cellular components. PMID:25658416

Diazo groups endure metabolism and enable chemoselectivity in cellulo.

PubMed

Andersen, Kristen A; Aronoff, Matthew R; McGrath, Nicholas A; Raines, Ronald T

2015-02-25

We introduce a stabilized diazo group as a reporter for chemical biology. ManDiaz, which is a diazo derivative of N-acetylmannosamine, is found to endure cellular metabolism and label the surface of a mammalian cell. There its diazo group can undergo a 1,3-dipolar cycloaddition with a strained alkyne, providing a signal comparable to that from the azido congener, ManNAz. The chemoselectivity of diazo and alkynyl groups enables dual labeling of cells that is not possible with azido and alkynyl groups. Thus, the diazo group, which is approximately half the size of an azido group, provides unique opportunities for orthogonal labeling of cellular components.

Effective biotransformation and detoxification of anthraquinone dye reactive blue 4 by using aerobic bacterial granules.

PubMed

Chaudhari, Ashvini U; Paul, Dhiraj; Dhotre, Dhiraj; Kodam, Kisan M

2017-10-01

Treatment of textile wastewater containing anthraquinone dye is quite a huge challenge due to its complex aromatic structure and toxicity. Present study deals with the degradation and detoxification of anthraquinone dye reactive blue 4 using aerobic bacterial granules. Bacterial granules effectively decolorized reactive blue 4 at wide range of pH (4.0-11.0) and temperature (20-55 °C) as well as decolorized and tolerated high concentration of reactive blue 4 dye upto 1000 mg l -1 with V max 6.16 ± 0.82 mg l -1 h -1 and K m 227 ± 41 mg l -1 . Metagenomics study evaluates important role of Clostridia, Actinobacteria, and Proteobacterial members in biotransformation and tolerance of high concentrations of reactive blue 4 dye. Up-regulation of xenobiotic degradation and environmental information processing pathways during dye exposure signifies their noteworthy role in dye degradation. Biotransformation of dye was confirmed by significant decrease in the values of total suspended solids, biological and chemical oxygen demand. The metabolites formed after biotransformation was characterized by FT-IR and GC-MS analysis. The reactive blue 4 dye was found to be phytotoxic, cytotoxic and genotoxic whereas its biotransformed product were non-toxic. This study comprehensively illustrates that, bacterial aerobic granules can be used for eco-friendly remediation and detoxification of wastewater containing high organic load of anthraquinone dye. Copyright © 2017 Elsevier Ltd. All rights reserved.

A nitrous acid biosynthetic pathway for diazo group formation in bacteria.

PubMed

Sugai, Yoshinori; Katsuyama, Yohei; Ohnishi, Yasuo

2016-02-01

Although some diazo compounds have bioactivities of medicinal interest, little is known about diazo group formation in nature. Here we describe an unprecedented nitrous acid biosynthetic pathway responsible for the formation of a diazo group in the biosynthesis of the ortho-diazoquinone secondary metabolite cremeomycin in Streptomyces cremeus. This finding provides important insights into the biosynthetic pathways not only for diazo compounds but also for other naturally occurring compounds containing nitrogen-nitrogen bonds.

The Cremeomycin Biosynthetic Gene Cluster Encodes a Pathway for Diazo Formation.

PubMed

Waldman, Abraham J; Pechersky, Yakov; Wang, Peng; Wang, Jennifer X; Balskus, Emily P

2015-10-12

Diazo groups are found in a range of natural products that possess potent biological activities. Despite longstanding interest in these metabolites, diazo group biosynthesis is not well understood, in part because of difficulties in identifying specific genes linked to diazo formation. Here we describe the discovery of the gene cluster that produces the o-diazoquinone natural product cremeomycin and its heterologous expression in Streptomyces lividans. We used stable isotope feeding experiments and in vitro characterization of biosynthetic enzymes to decipher the order of events in this pathway and establish that diazo construction involves late-stage N-N bond formation. This work represents the first successful production of a diazo-containing metabolite in a heterologous host, experimentally linking a set of genes with diazo formation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In vitro characterization of cutaneous immunotoxicity of immortalized human keratinocytes (HaCaT) exposed to reactive and disperse textile dyes.

PubMed

Leme, Daniela Morais; Sehr, Andrea; Grummt, Tamara; Gonçalves, Jenifer Pendiuk; Jacomasso, Thiago; Winnischofer, Sheila Maria Brochado; Potrich, Francine Bittencourt; Oliveira, Carolina Camargo de; Trindade, Edvaldo da Silva; de Oliveira, Danielle Palma

2018-05-01

Several synthetic dyes are used by textile industry for supplying the market of colored clothes. However, these chemicals have been associated with a variety of adverse human health effects, including textile dermatitis. Thus, there is a growing concern to identify textile dyes potentially as skin immunotoxicants. The aim of this in vitro study was to characterize the immunotoxic potential of reactive (Reactive Green 19 [RG19], Reactive Blue 2 [RB2], Reactive Black 5 [RB5]) and disperse (Disperse Red 1 [DR1]) textile dyes using a dermal cell line. For this purpose, a cell-based approach was conducted with immortalized human keratinocytes (KC) (HaCaT) using selected biomarkers of cutaneous inflammation including modulation of matrix metalloproteinases (MMP), oxidative stress such as reactive oxygen species (ROS) generation, and inflammatory cytokine profile. DR1 was the only dye able to trigger an immune response such as release of IL-12 cytokine, a potent co-stimulator of T helper 1 cell, which may be considered as a skin immunotoxicant. The reactive dyes including RB5 that were previously reported as skin sensitizers failed to induce inflammatory reactions under the conditions tested. The reactive dyes studied may pose a risk to human KC by induction of effects related to modulation of MMP-2 (RB5) and -9 (RB5 and RB2) and generation of ROS (RG19 and RB2). Thus, all these dyes need to be used with caution to avoid undesirable effects to consumers who may be exposed dermally.

Functionalizing the γ-Position of α-Diazo-β-ketoesters.

PubMed

Nguyen, Thu Q; Alqurafi, Maha; Edwards, Cash; Nguyen, Pauline; Kim, Jean; Casco, Samuel; Bennet, Maricka; Chiang, Christopher; Lohry, Maureen; Cox, Melina; Meshram, Byron; Le, Duyen; Kim, Eugene; Smriti, Snigdha; Oelschlaeger, Peter; Buynak, John D

2016-06-27

Although α-diazo-β-ketoesters are synthetically versatile intermediates, methodology for introducing this functionality into complex molecules is still limited, most frequently involving a carboxylic acid precursor, which is then activated and transformed into a β-ketoester, with the diazo group being subsequently added with a diazo transfer reagent. While introducing this highly functional moiety in a convergent one step process would be ideal, such an objective is limited by the relatively few studies which address functionalization of the α-diazo-β-ketoester at the γ-position. In the present investigation, we evaluate strategies, both new and established, for functionalizing α-diazo-β-ketoesters, particularly with regard to generating compounds prospectively useful in the synthesis of C1-substituted carbapenems. We report the first δ-aldehydo-α-diazo-β-ketoester as well as a method for its oxidation to the corresponding methyl ester, and the formation of a new substituted pyrazole under basic conditions.

Clinical and immunological investigations of respiratory disease in workers using reactive dyes.

PubMed Central

Docker, A; Wattie, J M; Topping, M D; Luczynska, C M; Newman Taylor, A J; Pickering, C A; Thomas, P; Gompertz, D

1987-01-01

A questionnaire survey of over 400 workers handling reactive dyes showed that over 15% had work related respiratory or nasal symptoms. Forty nine employees with symptoms were referred to chest clinics for detailed assessment. It was considered that in 19 the symptoms could be attributed to an irritant response to a variety of chemicals, including hydrochloric acid vapour, sulphur dioxide, and reactive dyes. Symptoms in 24 were attributed to an allergic reaction to a specific agent; in most (21) to one or more reactive dyes. Two patterns of allergic lower respiratory symptoms were identified; an immediate response of short duration and a longer lasting response, usually of several hours, sometimes accompanied by nocturnal asthma. A radioallergosorbent test (RAST) screen containing the most commonly used reactive dyes was used to detect specific IgE. Allergic symptoms to reactive dyes were strongly associated with specific IgE (17/21 employees) and atopy (18/21). Irritant symptoms were also associated with atopy (13/19) but only weakly associated with specific IgE (7/19). PMID:3651352

Stereoselective Synthesis of Highly Functionalized α-Diazo-β-ketoalkanoates via Catalytic Onepot Mukaiyama-Aldol Reactions

PubMed Central

Zhou, Lei; Doyle, Michael P.

2010-01-01

Methyl diazoacetoacetate undergoes zinc triflate catalyzed condensation with a broad selection of aldehydes to produce δ-siloxy-α-diazo-β-ketoalkanoates in good yield, and δ-hydroxy-α-diazo-β-ketoalkanoates are formed with high diastereoselectivity in reactions with α-diazo-β-ketopentanoate promoted by dibutylboron triflate. PMID:20102172

Enantioselective copper catalysed intramolecular C-H insertion reactions of α-diazo-β-keto sulfones, α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones; the influence of the carbene substituent.

PubMed

Shiely, Amy E; Slattery, Catherine N; Ford, Alan; Eccles, Kevin S; Lawrence, Simon E; Maguire, Anita R

2017-03-22

Enantioselectivities in C-H insertion reactions, employing the copper-bis(oxazoline)-NaBARF catalyst system, leading to cyclopentanones are highest with sulfonyl substituents on the carbene carbon, and furthermore, the impact is enhanced by increased steric demand on the sulfonyl substituent (up to 91%ee). Enantioselective intramolecular C-H insertion reactions of α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones are reported for the first time.

2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one: Another Utility for Electrophilic Trifluoromethylthiolation Reactions.

PubMed

Huang, Zhongyan; Okuyama, Kenta; Wang, Chen; Tokunaga, Etsuko; Li, Xiaorui; Shibata, Norio

2016-06-01

2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one (diazo-triflone) ( 2 ) is not only a building block but also a reagent. In this study, diazo-triflone, which was originally used for the synthesis of β-lactam triflones as a trifluoromethanesulfonyl (SO 2 CF 3 ) building block under catalyst-free thermal conditions, is redisclosed as an effective electrophilic trifluoromethylthiolation reagent under copper catalysis. A broad set of enamines, indoles, β-keto esters, pyrroles, and anilines were nicely transformed into corresponding trifluoromethylthio (SCF 3 ) compounds in good to high yields by diazo-triflone under copper catalysis via an electrophilic-type reaction. A coupling-type trifluoromethylthiolation reaction of aryl iodides was also realized by diazo-triflone in acceptable yields.

Effects of ultrasonic energy on dyeing of polyamide (microfibre)/Lycra blends.

PubMed

Merdan, Nigar; Akalin, Mehmet; Kocak, Dilara; Usta, Ismail

2004-04-01

Although ultrasonic energy is widely used cleaning and degreasing of parts and assemblies in automotive and other industries, the use of ultrasonic energy in an industrial scale for textile washing is very new. This is due to the complexity of controlling the combination of chemical and mechanical effects, whereas with degreasing of machine parts only the mechanical effects is applied. The use of ultrasonic energy in dyeing PA/Lycra fabrics with reactive dyes has been studied spectrophotometrically in this work. PA/Lycra (85/15) blends have been dyed using conventional and ultrasonic dyeing techniques with three reactive dyes containing different chromophore and reactive groups. The dyeing carried out conventionally and by the use of ultrasonic techniques. The results were compared in terms of percentage exhaustion; total dye transferred to the washing bath after dyeing and the fastness properties.

Color removal from acid and reactive dye solutions by electrocoagulation and electrocoagulation/adsorption processes.

PubMed

Bellebia, S; Kacha, S; Bouberka, Z; Bouyakoub, A Z; Derriche, Z

2009-04-01

In this study, electrocoagulation of Marine Blue Erionyl MR (acid dye) and electrocoagulation followed by adsorption of Brilliant Blue Levafix E-BRA (reactive dye) from aqueous solutions were investigated, using aluminum electrodes and granular activated carbon (GAC). In the electrocoagulation and adsorption of dyestuff solutions, the effects of current density, loading charge, pH, conductivity, stirring velocity, contact time, and GAC concentration were examined. The optimum conditions for the electrocoagulation process were identified as loading charges 7.46 and 1.49 F/m3, for a maximum abatement of 200 mg/L reactive and acid dye, respectively. The residual reactive dye concentration was completely removed with 700 mg/L GAC. The results of this investigation provide important data for the development of a combined process to remove significant concentrations of recalcitrant dyes from water, using moderate activated carbon energy and aluminum consumption, and thereby lowering the cost of treatment.

Mycoremediation of congo red dye by filamentous fungi.

PubMed

Bhattacharya, Sourav; Das, Arijit; G, Mangai; K, Vignesh; J, Sangeetha

2011-10-01

Azo, anthroquinone and triphenylmethane dyes are the major classes of synthetic colourants, which are difficult to degrade and have received considerable attention. Congo red, a diazo dye, is considered as a xenobiotic compound, and is recalcitrant to biodegradative processes. Nevertheless, during the last few years it has been demonstrated that several fungi, under certain environmental conditions, are able to transfer azo dyes to non toxic products using laccases. The aim of this work was to study the factors influencing mycoremediation of Congo red. Several basidiomycetes and deuteromycetes species were tested for the decolourisation of Congo red (0.05 g/l) in a semi synthetic broth at static and shaking conditions. Poor decolourisation was observed when the dye acted as the sole source of nitrogen, whereas semi synthetic broth supplemented with fertilizer resulted in better decolourisation. Decolourisation of Congo red was checked in the presence of salts of heavy metals such as mercuric chloride, lead acetate and zinc sulphate. Decolourisation parameters such as temperature, pH, and rpm were optimized and the decolourisation obtained at optimized conditions varied between 29.25- 97.28% at static condition and 82.1- 100% at shaking condition. Sodium dodecyl sulphate polyacrylamide gel electrophoretic analysis revealed bands with molecular weights ranging between 66.5 to 71 kDa, a characteristic of the fungal laccases. High efficiency decolourisation of Congo red makes these fungal forms a promising choice in biological treatment of waste water containing Congo red.

UV-Vis microspectrophotometry as a method of differentiation between cotton fibre evidence coloured with reactive dyes

NASA Astrophysics Data System (ADS)

Was-Gubala, Jolanta; Starczak, Roza

2015-05-01

The main purposes of this study was to assess the usefulness of microspectrophotometry (MSP), both in the ultraviolet (UV) and visible (Vis) range for discriminating single cotton fibres dyed with reactive dyes coming from the same manufacturer, as well as the possibility of evaluation of the concentration of dye in an examine fibre. This study utilised woven cotton fabrics dyed with different concentrations of one-compound reactive dyes with the commercial name Cibacron® (at present Novacron®) as the focus of the MSP analysis. The spectra were recorded in the UV-Vis range between 200 and 800 nm, in transmission mode. The results from this study illustrated that all of the analysed cotton samples dyed with reactive dyes were distinguishable between each other with the use of MSP, mostly in the visible, and also in ultraviolet range. The limit for applied MSP techniques was 0.18% of the concentration of a dye in the textile sample. The results indicate that based on the absorbance measurements for fibres constituting e.g. forensic traces it was not possible to estimate the concentration of the dye in the fibre because Beer's law did not obey. The intra-sample, and inter- sample variation, as well as dichroism effect in a case of a cotton fibres dyed with reactive dye were observed. On the basis of the results obtained for each analysed cotton sample, it was concluded that there was no correlation between colour uniformity in cotton fabric (changes in lightness, red/green and yellow/blue colour) and concentration of the reactive dye.

Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters† †Electronic supplementary information (ESI) available: Full procedures, computational details and characterization data. See DOI: 10.1039/c7sc04283c

PubMed Central

Thomas, Bryce N.; Moon, Patrick J.; Yin, Shengkang; Brown, Alex

2017-01-01

A well-defined Ir–allyl complex catalyzes the Z-selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E-products typically observed in metal-mediated coupling reactions to enable the synthesis of Z,E-dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir–carbene and Ir–allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E–H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt3. PMID:29629093

Effect of Reactive Black 5 azo dye on soil processes related to C and N cycling

PubMed Central

Rehman, Khadeeja; Sahar, Amna; Hussain, Sabir; Mahmood, Faisal; Siddique, Muhammad H.; Siddique, Muhammad A.; Rashid, Muhammad I.

2018-01-01

Azo dyes are one of the largest classes of synthetic dyes being used in textile industries. It has been reported that 15–50% of these dyes find their way into wastewater that is often used for irrigation purpose in developing countries. The effect of azo dyes contamination on soil nitrogen (N) has been studied previously. However, how does the azo dye contamination affect soil carbon (C) cycling is unknown. Therefore, we assessed the effect of azo dye contamination (Reactive Black 5, 30 mg kg−1 dry soil), bacteria that decolorize this dye and dye + bacteria in the presence or absence of maize leaf litter on soil respiration, soil inorganic N and microbial biomass. We found that dye contamination did not induce any change in soil respiration, soil microbial biomass or soil inorganic N availability (P > 0.05). Litter evidently increased soil respiration. Our study concludes that the Reactive Black 5 azo dye (applied in low amount, i.e., 30 mg kg−1 dry soil) contamination did not modify organic matter decomposition, N mineralization and microbial biomass in a silty loam soil.

Spectroscopic and thermal properties of short wavelength metal (II) complexes containing α-isoxazolylazo-β-diketones as co-ligands

NASA Astrophysics Data System (ADS)

Huang, Fuxin; Wu, Yiqun; Gu, Donghong; Gan, Fuxi

2005-10-01

Two new azo dyes of α-isoxazolylazo-β-diketones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni 2+ and Cu 2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl 3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability.

Rhodium Catalyzed Intramolecular C-H Insertion of α-Aryl-α-diazo Ketones

PubMed Central

Taber, Douglass F.; Tian, Weiwei

2011-01-01

Direct diazo transfer proceeds smoothly with α-aryl ketones. The derived α-aryl-α-diazo ketones cyclize efficiently with Rh catalysis to give the corresponding α-aryl cyclopentanones. PMID:17385917

Diazo compounds in the chemistry of fullerenes

NASA Astrophysics Data System (ADS)

Tuktarov, Airat R.; Dzhemilev, Usein M.

2010-09-01

Experimental and theoretical data on the reactions of different diazo compounds (diazomethane, its derivatives, cyclic diazo compounds and diazocarbonyl compounds) with fullerenes are summarized. The structures and stereochemistry of cycloadducts formed in these reactions are considered.

Metal-Diazo Radicals of α-Carbonyl Diazomethanes

PubMed Central

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-01-01

Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N∙ (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C∙, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C∙, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals. PMID:26960916

Metal-Diazo Radicals of α-Carbonyl Diazomethanes

NASA Astrophysics Data System (ADS)

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-03-01

Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

Metal-Diazo Radicals of α-Carbonyl Diazomethanes.

PubMed

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-03-10

Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [Rh(I)Cl(cod)]2, [Co(II)(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [Rh(I)Cl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N∙ (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C∙, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C∙, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

UV-Vis microspectrophotometry as a method of differentiation between cotton fibre evidence coloured with reactive dyes.

PubMed

Was-Gubala, Jolanta; Starczak, Roza

2015-05-05

The main purposes of this study was to assess the usefulness of microspectrophotometry (MSP), both in the ultraviolet (UV) and visible (Vis) range for discriminating single cotton fibres dyed with reactive dyes coming from the same manufacturer, as well as the possibility of evaluation of the concentration of dye in an examine fibre. This study utilised woven cotton fabrics dyed with different concentrations of one-compound reactive dyes with the commercial name Cibacron® (at present Novacron®) as the focus of the MSP analysis. The spectra were recorded in the UV-Vis range between 200 and 800nm, in transmission mode. The results from this study illustrated that all of the analysed cotton samples dyed with reactive dyes were distinguishable between each other with the use of MSP, mostly in the visible, and also in ultraviolet range. The limit for applied MSP techniques was 0.18% of the concentration of a dye in the textile sample. The results indicate that based on the absorbance measurements for fibres constituting e.g. forensic traces it was not possible to estimate the concentration of the dye in the fibre because Beer's law did not obey. The intra-sample, and inter- sample variation, as well as dichroism effect in a case of a cotton fibres dyed with reactive dye were observed. On the basis of the results obtained for each analysed cotton sample, it was concluded that there was no correlation between colour uniformity in cotton fabric (changes in lightness, red/green and yellow/blue colour) and concentration of the reactive dye. Copyright © 2015 Elsevier B.V. All rights reserved.

Photo-Electrochemical Treatment of Reactive Dyes in Wastewater and Reuse of the Effluent: Method Optimization

PubMed Central

Sala, Mireia; López-Grimau, Víctor; Gutiérrez-Bouzán, Carmen

2014-01-01

In this work, the efficiency of a photo-electrochemical method to remove color in textile dyeing effluents is discussed. The decolorization of a synthetic effluent containing a bi-functional reactive dye was carried out by applying an electrochemical treatment at different intensities (2 A, 5 A and 10 A), followed by ultraviolet irradiation. The combination of both treatments was optimized. The final percentage of effluent decolorization, the reduction of halogenated organic volatile compound and the total organic carbon removal were the determinant factors in the selection of the best treatment conditions. The optimized method was applied to the treatment of nine simulated dyeing effluents prepared with different reactive dyes in order to compare the behavior of mono, bi, and tri-reactive dyes. Finally, the nine treated effluents were reused in new dyeing processes and the color differences (DECMC (2:1)) with respect to a reference were evaluated. The influence of the effluent organic matter removal on the color differences was also studied. The reuse of the treated effluents provides satisfactory dyeing results, and an important reduction in water consumption and salt discharge is achieved. PMID:28788251

The Suitability of Diazo Films for Long Term Storage.

ERIC Educational Resources Information Center

Turner, Jeffrey H.

1988-01-01

Outlines the suitability of diazo film for the use of micrographics in libraries. Background information is provided, and diazo and silver film are compared. Film construction, environmental considerations, and fade resistance are discussed. (1 reference) (MES)

Synthesis of Cyclic α-Diazo-β-keto Sulfoxides in Batch and Continuous Flow.

PubMed

McCaw, Patrick G; Buckley, Naomi M; Eccles, Kevin S; Lawrence, Simon E; Maguire, Anita R; Collins, Stuart G

2017-04-07

Diazo transfer to β-keto sulfoxides to form stable isolable α-diazo-β-keto sulfoxides has been achieved for the first time. Both monocyclic and benzofused ketone derived β-keto sulfoxides were successfully explored as substrates for diazo transfer. Use of continuous flow leads to isolation of the desired compounds in enhanced yields relative to standard batch conditions, with short reaction times, increased safety profile, and potential to scale up.

Taming tosyl azide: the development of a scalable continuous diazo transfer process.

PubMed

Deadman, Benjamin J; O'Mahony, Rosella M; Lynch, Denis; Crowley, Daniel C; Collins, Stuart G; Maguire, Anita R

2016-04-07

Heat and shock sensitive tosyl azide was generated and used on demand in a telescoped diazo transfer process. Small quantities of tosyl azide were accessed in a 'one pot' batch procedure using shelf stable, readily available reagents. For large scale diazo transfer reactions tosyl azide was generated and used in a telescoped flow process, to mitigate the risks associated with handling potentially explosive reagents on scale. The in situ formed tosyl azide was used to rapidly perform diazo transfer to a range of acceptors, including β-ketoesters, β-ketoamides, malonate esters and β-ketosulfones. An effective in-line quench of sulfonyl azides was also developed, whereby a sacrificial acceptor molecule ensured complete consumption of any residual hazardous diazo transfer reagent. The telescoped diazo transfer process with in-line quenching was used to safely prepare over 21 g of an α-diazocarbonyl in >98% purity without any column chromatography.

Congo Red Stain Identifies Matrix Overproduction and Is an Indirect Measurement for c-di-GMP in Many Species of Bacteria.

PubMed

Jones, Christopher J; Wozniak, Daniel J

2017-01-01

Congo red is a diazo textile dye that has been used to visualize the production of amyloid fibers for nearly a century. Microbiological applications were later developed, especially in identifying strains that produce amyloid appendages called curli and overexpressing polysaccharides in the biofilm matrix. The second messenger cyclic diguanylate (c-di-GMP) regulates the production of biofilm matrix polysaccharides, and therefore Congo red staining of samples can be utilized as an indirect measurement of elevated c-di-GMP production in bacteria. Congo red allows the identification of strains producing high c-di-GMP in an inexpensive, quantitative, and high-throughput manner.

3D-QSPR Method of Computational Technique Applied on Red Reactive Dyes by Using CoMFA Strategy

PubMed Central

Mahmood, Uzma; Rashid, Sitara; Ali, S. Ishrat; Parveen, Rasheeda; Zaheer-ul-Haq; Ambreen, Nida; Khan, Khalid Mohammed; Perveen, Shahnaz; Voelter, Wolfgang

2011-01-01

Cellulose fiber is a tremendous natural resource that has broad application in various productions including the textile industry. The dyes, which are commonly used for cellulose printing, are “reactive dyes” because of their high wet fastness and brilliant colors. The interaction of various dyes with the cellulose fiber depends upon the physiochemical properties that are governed by specific features of the dye molecule. The binding pattern of the reactive dye with cellulose fiber is called the ligand-receptor concept. In the current study, the three dimensional quantitative structure property relationship (3D-QSPR) technique was applied to understand the red reactive dyes interactions with the cellulose by the Comparative Molecular Field Analysis (CoMFA) method. This method was successfully utilized to predict a reliable model. The predicted model gives satisfactory statistical results and in the light of these, it was further analyzed. Additionally, the graphical outcomes (contour maps) help us to understand the modification pattern and to correlate the structural changes with respect to the absorptivity. Furthermore, the final selected model has potential to assist in understanding the charachteristics of the external test set. The study could be helpful to design new reactive dyes with better affinity and selectivity for the cellulose fiber. PMID:22272108

Adsorption of dissolved Reactive red dye from aqueous phase onto activated carbon prepared from agricultural waste.

PubMed

Senthilkumaar, S; Kalaamani, P; Porkodi, K; Varadarajan, P R; Subburaam, C V

2006-09-01

The adsorption of Reactive red dye (RR) onto Coconut tree flower carbon (CFC) and Jute fibre carbon (JFC) from aqueous solution was investigated. Adsorption studies were carried out at different initial dye concentrations, initial solution pH and adsorbent doses. The kinetic studies were also conducted; the adsorption of Reactive red onto CFC and JFC followed pseudosecond-order rate equation. The effective diffusion coefficient was evaluated to establish the film diffusion mechanism. Quantitative removal of Reactive red dye was achieved at strongly acidic conditions for both the carbons studied. The adsorption isotherm data were fitted well to Langmuir isotherm and the adsorption capacity were found to be 181.9 and 200 mg/g for CFC and JFC, respectively. The overall rate of dye adsorption appeared to be controlled by chemisorption, in this case in accordance with poor desorption studies.

Fluorogenic Strain-Promoted Alkyne-Diazo Cycloadditions

PubMed Central

Friscourt, Frédéric; Fahrni, Christoph J.; Boons, Geert-Jan

2016-01-01

Fluorogenic reactions in which non- or weakly-fluorescent reagents produce highly fluorescent products are attractive for detecting a broad range of compounds in the fields of bio-conjugation and material sciences. We report here that Fl-DIBO, a dibenzocyclooctyne derivative modified with a cyclopropenone moiety, can undergo fast strain-promoted cycloadditions under catalyst-free conditions with azides, nitrones, nitrile oxides as well as mono- and disubstituted diazo-derivatives. While the reaction with nitrile oxides, nitrones and disubstituted diazo compounds gave cycloadducts with low quantum yield, monosubstituted diazo reagents produced 1H-pyrazole derivatives that exhibited a ~160-fold fluorescence enhancement over Fl-DIBO combined with a greater than 10,000-fold increase in brightness. Concluding from quantum chemical calculations, fluorescence quenching of 3H-pyrazoles, which are formed by reaction with disubstituted diazo-derivatives, is likely due to the presence of energetically low-lying (n,π*) states. The fluorogenic probe Fl-DIBO was successfully employed for the labeling of diazo-tagged proteins without detectable background signal. Diazo-derivatives are emerging as attractive reporters for the labeling of biomolecules and the studies presented here demonstrate that Fl-DIBO can be employed for visualizing such biomolecules without the need for probe washout. PMID:26330090

40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

Code of Federal Regulations, 2010 CFR

2010-07-01

... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting under...

40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

Code of Federal Regulations, 2011 CFR

2011-07-01

... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting under...

Rh(III)-Catalyzed C-H Activation of Benzoylacetonitriles and Tandem Cyclization with Diazo Compounds to Substituted Benzo[ de]chromenes.

PubMed

Fang, Feifei; Zhang, Chunmei; Zhou, Chaofan; Li, Yazhou; Zhou, Yu; Liu, Hong

2018-04-06

Rh (III)-catalyzed C-H activation of benzoylacetonitriles in coupling with diazo compounds was developed to synthesize diversified substituted benzo[ de]chromenes via a formal (4 + 2) cycloaddition with a diazo compound and subsequent tandem (4 + 2) cycloaddition with another diazo compound. Intriguingly, synthesis of substituted benzo[ de]chromenes and their decarboxylation products could be realized by controlling the reaction conditions. These reactions have a broad range of substrates, moderate to good yields, and high regioselectivity.

Gold(I)-catalyzed diazo coupling: strategy towards alkene formation and tandem benzannulation.

PubMed

Zhang, Daming; Xu, Guangyang; Ding, Dong; Zhu, Chenghao; Li, Jian; Sun, Jiangtao

2014-10-06

A gold(I)-catalyzed cross-coupling of diazo compounds to afford tetrasubstituted alkenes has been developed by taking advantage of a trivial electronic difference between two diazo substrates. A N-heterocyclic-carbene-derived gold complex is the most effective catalyst for this transformation. Based on this new strategy, a gold(I)-initiated benzannulation has been achieved through a tandem reaction involving a diazo cross-coupling, 6π electrocyclization, and oxidative aromatization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zinc-Catalyzed Synthesis of Conjugated Dienoates through Unusual Cross-Couplings of Zinc Carbenes with Diazo Compounds.

PubMed

Mata, Sergio; González, María J; González, Jesús; López, Luis A; Vicente, Rubén

2017-01-23

Zinc-catalyzed selective cross-coupling of two carbene sources, such as vinyl diazo compounds and enynones, enabled the synthesis of conjugated dienoate derivatives. This reaction involved the unprecedented coupling of a zinc furyl carbene with vinyl diazo compounds through the γ-carbon. Alternatively, dienoates were also prepared by a commutative cross-coupling of zinc vinyl carbenes generated from cyclopropenes and simple diazo compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Homologation Reaction of Ketones with Diazo Compounds.

PubMed

Candeias, Nuno R; Paterna, Roberta; Gois, Pedro M P

2016-03-09

This review covers the addition of diazo compounds to ketones to afford homologated ketones, either in the presence or in the absence of promoters or catalysts. Reactions with diazoalkanes, aryldiazomethanes, trimethylsilyldiazomethane, α-diazo esters, and disubstituted diazo compounds are covered, commenting on the complex regiochemistry of the reaction and the nature of the catalysts and promoters. The recent reports on the enantioselective version of ketone homologation reactions are gathered in one section, followed by reports on the use of cyclic ketones ring expansion in total synthesis. Although the first reports of this reaction appeared in the literature almost one century ago, the recent achievements, in particular, for the asymmetric version, forecast the development of new breakthroughs in the synthetically valuable field of diazo chemistry.

Techniques for using diazo materials in remote sensor data analysis

NASA Technical Reports Server (NTRS)

Whitebay, L. E.; Mount, S.

1978-01-01

The use of data derived from LANDSAT is facilitated when special products or computer enhanced images can be analyzed. However, the facilities required to produce and analyze such products prevent many users from taking full advantages of the LANDSAT data. A simple, low-cost method is presented by which users can make their own specially enhanced composite images from the four band black and white LANDSAT images by using the diazo process. The diazo process is described and a detailed procedure for making various color composites, such as color infrared, false natural color, and false color, is provided. The advantages and limitations of the diazo process are discussed. A brief discussion interpretation of diazo composites for land use mapping with some typical examples is included.

Dye-ligand affinity systems.

PubMed

Denizli, A; Pişkin, E

2001-10-30

Dye-ligands have been considered as one of the important alternatives to natural counterparts for specific affinity chromatography. Dye-ligands are able to bind most types of proteins, in some cases in a remarkably specific manner. They are commercially available, inexpensive, and can easily be immobilized, especially on matrices bearing hydroxyl groups. Although dyes are all synthetic in nature, they are still classified as affinity ligands because they interact with the active sites of many proteins mimicking the structure of the substrates, cofactors, or binding agents for those proteins. A number of textile dyes, known as reactive dyes, have been used for protein purification. Most of these reactive dyes consist of a chromophore (either azo dyes, anthraquinone, or phathalocyanine), linked to a reactive group (often a mono- or dichlorotriazine ring). The interaction between the dye ligand and proteins can be by complex combination of electrostatic, hydrophobic, hydrogen bonding. Selection of the supporting matrix is the first important consideration in dye-affinity systems. There are several methods for immobilization of dye molecules onto the support matrix, in which usually several intermediate steps are followed. Both the adsorption and elution steps should carefully be optimized/designed for a successful separation. Dye-affinity systems in the form of spherical sorbents or as affinity membranes have been used in protein separation.

Bent CNN bond of diazo compounds, RR'(Cdbnd N+dbnd N-)

NASA Astrophysics Data System (ADS)

Akita, Motoko; Takahashi, Mai; Kobayashi, Keiji; Hayashi, Naoto; Tukada, Hideyuki

2013-02-01

The reaction of ninhydrin with benzophenone hydrazone afforded 2-diazo-3-diphenylmethylenehydrazono-1-indanone 1 and 2-diazo-1,3-bis(diphenylmethylenehydrazono)indan 2. X-ray crystal structure analyses of these products showed that the diazo functional group Cdbnd N+dbnd N- of 1 is bent by 172.9°, while that of 2 has a linear geometry. The crystal structure data of diazo compounds have been retrieved from the Cambridge Structural Database (CSD), which hit 177 entries to indicate that the angle of 172.9° in 1 lies in one of the most bent structures. The CSD search also indicated that diazo compounds consisting of a distorted diazo carbon tend to bend the Cdbnd N+dbnd N- bond. On the basis of DFT calculations (B3LYP/6-311++G(d,p)) of model compounds, it was revealed that the bending of the CNN bond is principally induced by steric factors and that the neighboring carbonyl group also plays a role in bending toward the carbonyl side owing to an electrostatic attractive interaction. The potential surface along the path of Cdbnd N+dbnd N- bending in 2-diazopropane shows a significantly shallow profile with only 4 kcal/mol needed to bend the Cdbnd N+dbnd N- bond from 180° to 160°. Thus, the bending of the diazo group in 1 is reasonable as it is provided with all of the factors for facile bending disclosed in this investigation.

Removal of dissolved textile dyes from wastewater by a compost sorbent

USGS Publications Warehouse

Tsui, L.S.; Roy, W.R.; Cole, M.A.

2003-01-01

The objective of this study was to evaluate the potential for treating dye-contaminated waste streams by sorption using compost as a low-cost sorbent. A mature, thermophilic compost sample was used to sorb CI Acid Black 24, CI Acid Orange 74, CI Basic Blue 9, CI Basic Green 4, CI Direct Blue 71, CI Direct Orange 39, CI Reactive Orange 16 and CI Reactive Red 2 from solution using a batch-sorption method. With the exception of the two reactive dyes, the sorption kinetics were favourable for a continuous-flow treatment process with the compost-dye mixtures reaching a steady state within 3-5 h. Based on limited comparisons, the affinity of the compost for each dye appeared to be competitive with other non-activated carbon sorbents. The results suggest that additional research on using compost as a sorbent for dye-contaminated solutions is warranted.

A mild, efficient method for the oxidation of α-diazo-β-hydroxyesters to α-diazo-β-ketoesters

PubMed Central

Li, Puhui; Majireck, Max M.; Korboukh, Ilia; Weinreb, Steven M.

2008-01-01

A wide variety of α-diazo-β-ketoesters can be prepared in good overall yields via a two-step sequence involving addition of ethyl lithiodiazoacetate to aliphatic, aromatic and conjugated aldehydes followed by mild oxidation with the Dess-Martin periodinane. PMID:19421308

1,3-Dipolar Cycloadditions of Diazo Compounds in the Presence of Azides.

PubMed

Aronoff, Matthew R; Gold, Brian; Raines, Ronald T

2016-04-01

The diazo group has untapped utility in chemical biology. The tolerance of stabilized diazo groups to cellular metabolism is comparable to that of azido groups. However, chemoselectivity has been elusive, as both groups undergo 1,3-dipolar cycloadditions with strained alkynes. Removing strain and tuning dipolarophile electronics yields diazo group selective 1,3-dipolar cycloadditions that can be performed in the presence of an azido group. For example, diazoacetamide but not its azido congener react with dehydroalanine residues, as in the natural product nisin.

Rh(III)-Catalyzed Synthesis of N-Unprotected Indoles from Imidamides and Diazo Ketoesters via C-H Activation and C-C/C-N Bond Cleavage.

PubMed

Qi, Zisong; Yu, Songjie; Li, Xingwei

2016-02-19

The synthesis of N-unprotected indoles has been realized via Rh(III)-catalyzed C-H activation/annulation of imidamides with α-diazo β-ketoesters. The reaction occurs with the release of an amide coproduct, which originates from both the imidamide and the diazo as a result of C═N cleavage of the imidamide and C-C(acyl) cleavage of the diazo. A rhodacyclic intermediate has been isolated and a plausible mechanism has been proposed.

A chiral Brønsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines.

PubMed

Unhale, Rajshekhar A; Sadhu, Milon M; Ray, Sumit K; Biswas, Rayhan G; Singh, Vinod K

2018-04-03

A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.

Silver-mediated direct trifluoromethoxylation of α-diazo esters via the (-)OCF3 anion.

PubMed

Zha, Gao-Feng; Han, Jia-Bin; Hu, Xiao-Qian; Qin, Hua-Li; Fang, Wan-Yin; Zhang, Cheng-Pan

2016-06-14

Silver-mediated direct trifluoromethoxylation of α-diazo esters and ketosteroid was disclosed. The reactions of alkyl α-diazo arylacetates with AgOCF3 or CF3SO2OCF3/AgF at -30 to 10 °C under a N2 atmosphere provided α-trifluoromethoxyl arylacetates in up to 90% yield, while alkyl α-diazo vinylacetates reacting with CF3SO2OCF3/AgF or AgOCF3 afforded γ-trifluoromethoxyl α,β-unsaturated esters in up to 94% yield. The α-diazo ketosteroid was also trifluoromethoxylated under the standard reaction conditions. This protocol allows for an effective and convenient access to a large number of synthetic building blocks, which are promising in the development of new functional OCF3-molecules.

The Generation of Diazo Compounds in Continuous-Flow.

PubMed

Hock, Katharina J; Koenigs, Rene M

2018-03-25

Toxic, cancerogenic and explosive - these attributes are typically associated with diazo compounds. Nonetheless, diazo compounds are nowadays a highly demanded class of reagents for organic synthesis, yet the concerns with regards to safe and scalable transformations of these compounds are still exceptionally high. Lately, the research area of the continuous-flow synthesis of diazo compounds attracted significant interest and a whole variety of protocols for their "on-demand" preparation have been realized to date. This concept article focuses on the recent developments using continuous-flow technologies to access diazo compounds; thus minimizing risks and hazards when working with this particular class of compounds. In this article we discuss these concepts and highlight different pre-requisites to access and to perform downstream functionalization reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorogenic Strain-Promoted Alkyne-Diazo Cycloadditions.

PubMed

Friscourt, Frédéric; Fahrni, Christoph J; Boons, Geert-Jan

2015-09-28

Fluorogenic reactions, in which non- or weakly fluorescent reagents produce highly fluorescent products, are attractive for detecting a broad range of compounds in the fields of bioconjugation and material sciences. Herein, we report that a dibenzocyclooctyne derivative modified with a cyclopropenone moiety (Fl-DIBO) can undergo fast strain-promoted cycloaddition reactions under catalyst-free conditions with azides, nitrones, nitrile oxides, as well as mono- and disubstituted diazo-derivatives. Although the reaction with nitrile oxides, nitrones, and disubstituted diazo compounds gave cycloadducts with low quantum yield, monosubstituted diazo reagents produced 1H-pyrazole derivatives that exhibited an approximately 160-fold fluorescence enhancement over Fl-DIBO combined with a greater than 10,000-fold increase in brightness. Concluding from quantum chemical calculations, fluorescence quenching of 3H-pyrazoles, which are formed by reaction with disubstituted diazo-derivatives, is likely due to the presence of energetically low-lying (n,π*) states. The fluorogenic probe Fl-DIBO was successfully employed for the labeling of diazo-tagged proteins without detectable background signal. Diazo-derivatives are emerging as attractive reporters for the labeling of biomolecules, and the studies presented herein demonstrate that Fl-DIBO can be employed for visualizing such biomolecules without the need for probe washout. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ozonation of exhausted dark shade reactive dye bath for reuse.

PubMed

Sundrarajan, M; Vishnu, G; Joseph, Kurian

2006-10-01

Exhausted reactive dye bath of dark shades were collected from cotton knit wear dyeing units in Tirupur. Ozonation was conducted in a column reactor system fed with ozone at the rate of 0.16 g/min to assess its efficiency in reducing the color, chemical oxygen demand and total organic carbon. The potential of the decolorized dye bath for its repeated reuse was also analyzed. The results from the reusability studies indicate that the dyeing quality was not affected by the reuse of decolorized dye bath for two successive cycles. Complete decolorization of the effluent was achieved in 60 minutes contact time at an ozone consumption of 183 mg/L for Red, 175 for Navy Blue and 192 for Green shades respectively. The corresponding COD removal was 60%, 54% and 63% for the three shades while TOC removal efficiency was 59%, 55% and 62% respectively. It is concluded that ozonation is efficient in decolorization of exhausted dye bath effluents containing conventional reactive dyes. However, the corresponding removal of COD from the textile effluent was not significant.

Oxidation of Levafix CA reactive azo-dyes in industrial wastewater of textile dyeing by electro-generated Fenton's reagent.

PubMed

El-Desoky, Hanaa S; Ghoneim, Mohamed M; El-Sheikh, Ragaa; Zidan, Naglaa M

2010-03-15

The indirect electrochemical removal of pollutants from effluents has become an attractive method in recent years. Removal (decolorization and mineralization) of Levafix Blue CA and Levafix Red CA reactive azo-dyes from aqueous media by electro-generated Fenton's reagent (Fe(2+)/H(2)O(2)) using a reticulated vitreous carbon cathode and a platinum gauze anode was optimized. Progress of oxidation (decolorization and mineralization) of the investigated azo-dyes with time of electro-Fenton's reaction was monitored by UV-visible absorbance measurements, Chemical oxygen demand (COD) removal and HPLC analysis. The results indicated that the electro-Fenton's oxidation system is efficient for treatment of such types of reactive dyes. Oxidation of each of the investigated azo-dyes by electro-generated Fenton's reagent up to complete decolorization and approximately 90-95% mineralization was achieved. Moreover, the optimized electro-Fenton's oxidation was successfully applied for complete decolorization and approximately 85-90% mineralization of both azo-dyes in real industrial wastewater samples collected from textile dyeing house at El-Mahalla El-Kobra, Egypt. (c) 2009 Elsevier B.V. All rights reserved.

Removal of Direct Red 23 from aqueous solution using corn stalks: Isotherms, kinetics and thermodynamic studies

NASA Astrophysics Data System (ADS)

Fathi, M. R.; Asfaram, A.; Farhangi, A.

2015-01-01

The objective of this study was to assess the suitability and efficiency of corn stalk (CS) for the removal of diazo dye Direct Red 23 (DR23) from aqueous solutions. The effect of different variables in the batch method as a function of solution pH, contact time, initial dye concentration, CS amount, temperature, and so forth by the optimization method has been investigated. The color reduction was monitored by spectrophotometry at 503 nm before and after DR23 adsorption on the CS, and the removal percentage was calculated using the difference in absorbance. The sorption processes followed the pseudo second order in addition to intraparticle diffusion kinetics models with a good correlation coefficient with the overall entire adsorption of DR23 on adsorbent. The experimental equilibrium data were tested by four widely used isotherm models namely, Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich (D-R). It was found that adsorption of DR23 on CS well with the Freindlich isotherm model, implying monolayer coverage of dye molecules onto the surface of the adsorbent. More than 99% removal efficiency was obtained within 10 min at adsorbent dose of 0.2 g for initial dye concentration of 10-90 mg L-1 at pH 3. Various thermodynamic parameters, such as Gibbs free energy, entropy, and enthalpy, of the ongoing adsorption process have been calculated. Judgment based on the obtained results of thermodynamic values shows the spontaneous and endothermic nature adsorption processes on adsorbent.

Mediator-assisted decolorization and detoxification of textile dyes/dye mixture by Cyathus bulleri laccase.

PubMed

Chhabra, Meenu; Mishra, Saroj; Sreekrishnan, T R

2008-12-01

Laccase from basidiomycete fungus Cyathus bulleri was evaluated for its ability to decolorize a number of reactive and acidic dyes in the presence of natural and synthetic mediators. The extent of decolorization was monitored at different mediator/dye concentrations and incubation time. Among the synthetic mediators, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) was effective at low mediator/dye ratios and resulted in 80-95% decolorization at rates that varied from 226 +/- 4 nmol min(-1) mg(-1) for Reactive Orange 1 to 1,333 +/- 15 nmol min(-1) mg(-1) for Reactive Red 198. Other synthetic mediators like 1-hydroxybenzotriazole and violuric acid showed both concentration- and time-dependent increases in percent decolorization. Natural mediators like vanillin, on the other hand, were found to be less effective on all the dyes except Reactive Orange 1. Computed rates of decolorization were about twofold lower than that with ABTS. The laccase-ABTS system also led to nearly 80% decolorization for the simulated dye mixture. No clear correlation between laccase activity on the mediator and its ability to decolorize dyes was found, but pH had a significant effect: Optimum pH for decolorization coincided with the optimum pH for mediator oxidation. The treated samples were also evaluated for toxicity in model microbial systems. The laccase-mediator system appears promising for treatment of textile wastewaters.

Reactive carbon-chain molecules: synthesis of 1-diazo-2,4-pentadiyne and spectroscopic characterization of triplet pentadiynylidene (H-C[triple bond]C-:C-C[triple bond]C-H).

PubMed

Bowling, Nathan P; Halter, Robert J; Hodges, Jonathan A; Seburg, Randal A; Thomas, Phillip S; Simmons, Christopher S; Stanton, John F; McMahon, Robert J

2006-03-15

1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C[triple bond]C-:C-C[triple bond]C-H). Theory predicts an axially symmetric (D(infinity h)) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (absolute value(D/hc) = 0.6157 cm(-1), absolute value(E/hc) = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O2-doped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

Reactive Black 5 dye degradation using filters of smuggled cigarette modified with Fe3.

PubMed

Glugoski, Letícia Polli; de Jesus Cubas, Paloma; Fujiwara, Sérgio Toshio

2017-03-01

This study presents an attempt to solve two serious environmental problems: the generation of toxic effluents and solid waste disposal. The work proposes recycling cigarette filters with the purpose of degrading reactive dyes, which are used in the textile industry. Filters of smuggled cigarettes were recycled through Fe 3+ immobilization on their surface. The material obtained was characterized through Fourier transform infrared spectroscopy (FTIR), atomic absorption spectroscopy (AAS), scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS), and ultraviolet-visible spectroscopy (UV-vis). The factorial design revealed that the most suitable conditions for the degradation of Reactive Black 5 dye were obtained by using 1 g of material at pH 3.0 in a 100 mg L -1 hydrogen peroxide solution. The material showed excellent performance in the Reactive Black 5 dye degradation process; in 60 min, 99.09 % dye was removed. At pH 7.0, the dye degradation was 72.67 %, indicating that the material prepared can be used at pH values greater than 3.0 without the occurrence of hydrated Fe 3+ oxide precipitation. Furthermore, the material showed no loss of catalytic activity after three degradation studies.

Sugarcane bagasse powder as biosorbent for reactive red 120 removals from aqueous solution

NASA Astrophysics Data System (ADS)

Ahmad, S.; Wong, Y. C.; Veloo, K. V.

2018-04-01

Reactive red 120 is used as a textile dye for fabric coloring. The dye waste is produced during textile finishing process subsequently released directly to water bodies which giving harmful effects to the environment due to the carcinogenic characteristic. Adsorption process becomes an effective treatment to treat textile dye. This research emphasizes the treatment of textile dye namely reactive red 120 (RR120) by using sugarcane bagasse powder. The batch study was carried out under varying parameters such as 60 minutes contact time, pH (1-8), dye concentration (5-25 mg/L), particle size (125-500 μm) and biosorbent dosage (0.01-0.2 g/L). The maximum adsorption percentage of RR120 was 94.62%. The adsorption of dye was increased with the decreasing of pH, initial dye concentration and particle size. Sugarcane bagasse powder as low-cost biosorbent was established using Fourier Transform Infrared (FTIR) and scanning electron microscopy (SEM). This locally agricultural waste could be upgraded into useful material which is biosorbent that promising for decolorization of colored textile wastewater.

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

PubMed

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.

A Versatile Route to Unstable Diazo Compounds via Oxadiazolines and their Use in Aryl–Alkyl Cross‐Coupling Reactions

PubMed Central

Greb, Andreas; Poh, Jian‐Siang; Greed, Stephanie; Battilocchio, Claudio; Pasau, Patrick; Blakemore, David C.

2017-01-01

Abstract Coupling of readily available boronic acids and diazo compounds has emerged recently as a powerful metal‐free carbon–carbon bond forming method. However, the difficulty in forming the unstable diazo compound partner in a mild fashion has hitherto limited their general use and the scope of the transformation. Here, we report the application of oxadiazolines as precursors for the generation of an unstable family of diazo compounds using flow UV photolysis and their first use in divergent protodeboronative and oxidative C(sp2)−C(sp3) cross‐coupling processes, with excellent functional‐group tolerance. PMID:29088512

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

PubMed

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.

Antibody labeling with Remazol Brilliant Violet 5R, a vinylsulphonic reactive dye.

PubMed

Ferrari, Alejandro; Friedrich, Adrián; Weill, Federico; Wolman, Federico; Leoni, Juliana

2013-01-01

Colloidal gold is the first choice for labeling antibodies to be used in Point Of Care Testing. However, there are some recent reports on a family of textile dyes-named "reactive dyes"-being suitable for protein labeling. In the present article, protein labeling conditions were optimized for Remazol Brilliant Violet 5R, and the sensitivity of the labeled antibodies was assessed and compared with that of colloidal-gold labeled antibodies. Also, the accelerated stability was explored. Optimal conditions were pH 10.95, dye:Ab molar ratio of 264 and an incubation time of 132 min. Labeled antibodies were stable, and could be successfully used in a slot blot assay, detecting as low as 400 ng/mL. Therefore, the present work demonstrates that vinylsulphonic reactive dyes can be successfully used to label antibodies, and are excellent candidates for the construction of a new generation of Point of Care Testing kits.

Rh-Catalyzed Intermolecular Reactions of α-Alkyl-α-Diazo Carbonyl Compounds with Selectivity over β-Hydride Migration

PubMed Central

DeAngelis, Andrew; Panish, Robert; Fox, Joseph M.

2016-01-01

CONSPECTUS Rh-carbenes derived from α-diazocarbonyl compounds have found broad utility across a remarkable range of reactivity, including cyclopropanation, cyclopropenation, C–H insertions, heteroatom–H insertions, and ylide forming reactions. However, in contrast to α-aryl or α-vinyl-α-diazocarbonyl compounds, the utility of α-alkyl-α-diazocarbonyl compounds had been moderated by the propensity of such compounds to undergo intramolecular β-hydride migration to give alkene products. Especially challenging had been intermolecular reactions involving α-alkyl-α-diazocarbonyl compounds. PMID:26689221

A Non-Diazo Approach to α-Oxo Gold Carbenes via Gold-Catalyzed Alkyne Oxidation

PubMed Central

2015-01-01

For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C–H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The intermolecular approach offers excellent synthetic flexibility because no tethering of the oxidant is required, and its reduced form is not tangled with the product. We were the first research group to develop this strategy, through the use of pyridine/quinolone N-oxides as the external oxidants. In this manner, we can effectively make a C–C triple bond a surrogate of an α-diazo carbonyl moiety in various gold catalyses. With terminal alkynes, we demonstrated that we can efficiently trap exclusively formed terminal carbene centers by internal nucleophiles en route to the formation of cyclic products, including strained oxetan-3-ones and azetidin-3-ones, and by external nucleophiles when a P,N-bidentate ligand is coordinated to gold. With internal alkynes, we generated synthetically useful regioselectivities in the generation of the α-oxo gold carbene moiety, which enables expedient formation of versatile enone products. Other research groups have also applied this strategy en route to versatile synthetic methods. The α-oxo gold carbenes appear to be more electrophilic than their Rh counterpart, which many chemists have focused on in a large array of excellent work on metal carbene chemistry. The ease of accessing the reactive gold carbenes opens up a vast area for developing new synthetic methods that would be distinctively different from the known Rh chemistry and promises to generate a new round of “gold rush”. PMID:24428596

A non-diazo approach to α-oxo gold carbenes via gold-catalyzed alkyne oxidation.

PubMed

Zhang, Liming

2014-03-18

For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C-H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The intermolecular approach offers excellent synthetic flexibility because no tethering of the oxidant is required, and its reduced form is not tangled with the product. We were the first research group to develop this strategy, through the use of pyridine/quinolone N-oxides as the external oxidants. In this manner, we can effectively make a C-C triple bond a surrogate of an α-diazo carbonyl moiety in various gold catalyses. With terminal alkynes, we demonstrated that we can efficiently trap exclusively formed terminal carbene centers by internal nucleophiles en route to the formation of cyclic products, including strained oxetan-3-ones and azetidin-3-ones, and by external nucleophiles when a P,N-bidentate ligand is coordinated to gold. With internal alkynes, we generated synthetically useful regioselectivities in the generation of the α-oxo gold carbene moiety, which enables expedient formation of versatile enone products. Other research groups have also applied this strategy en route to versatile synthetic methods. The α-oxo gold carbenes appear to be more electrophilic than their Rh counterpart, which many chemists have focused on in a large array of excellent work on metal carbene chemistry. The ease of accessing the reactive gold carbenes opens up a vast area for developing new synthetic methods that would be distinctively different from the known Rh chemistry and promises to generate a new round of "gold rush".

Visible light photocatalytic activities of template free porous graphitic carbon nitride-BiOBr composite catalysts towards the mineralization of reactive dyes

NASA Astrophysics Data System (ADS)

Kanagaraj, Thamaraiselvi; Thiripuranthagan, Sivakumar; Paskalis, Sahaya Murphin Kumar; Abe, Hideki

2017-12-01

Template free porous g-C3N4 (pGCN) and flower like bismuth oxybromide catalysts were synthesized by poly condensation and precipitation methods respectively. Various weight percentages of porous GCN-BiOBr composite catalysts (x% pGCN-BiOBr where x = 5, 10, 30, 50 & 70 wt% of pGCN) were synthesized by impregnation method. All the synthesized catalysts were characterized by X-Ray diffractometer, Fourier transform infrared spectrophotometer, BET surface area analyzer, UV Visible diffuse reflectance spectrophotometer, X-Ray photoelectron spectrophotometer, SEM with Energy dispersive X-ray analyzer (SEM/EDAX) and elemental mapping, Transmission electron microscope, Photoluminescence spectrophotometer and Electrochemical impedance. Photocatalytic degradation of all the synthesized catalysts were tested towards the harmful reactive dyes such as reactive blue 198 (RB 198), reactive black 5 (RB 5) and reactive yellow 145 (RY 145) in presence of visible irradiation. Among the catalysts 30% pGCN-BiOBr resulted in the highest photocatalytic activity towards the degradation of all the three dyes in presence of UV, visible and solar irradiations. Kinetics studies on the photocatalytic mineralization of dyes indicated that it followed pseudo first order. HPLC, TOC and COD studies confirm that the dyes are mineralized into CO2, water and mineral salts.

Novel cyanine dyes with vinylsulfone group for labeling biomolecules.

PubMed

Park, Jin Woo; Kim, YoungSoo; Lee, Kee-Jung; Kim, Dong Jin

2012-03-21

Novel vinylsulfone cyanine dyes (em. 550-850 nm) were designed and synthesized for fluorescent labeling of biomolecules via 1,2-addition reaction in aqueous conditions. Due to the virtue of chemical structures of both fluorophore and reactive group, these dyes could be significantly stable and reactive in various aqueous/organic conditions. A wide variety of pH, temperature, buffer concentration, and protein were tested for the optimal labeling condition.

The toxicity of textile reactive azo dyes after hydrolysis and decolourisation.

PubMed

Gottlieb, Anna; Shaw, Chris; Smith, Alan; Wheatley, Andrew; Forsythe, Stephen

2003-02-27

The toxicity of C.I. Reactive Black 5 and three Procion dyes, as found in textile effluents, was determined using the bioluminescent bacterium Vibrio fischeri. Hydrolysed Reactive Black had a slightly greater toxicity than the parent form (EC(50) 11.4+/-3.68 and 27.5+/-4.01 mg l(-1), respectively). A baffled bioreactor with anaerobic and aerobic compartments was used to decolourise hydrolysed Reactive Black 5 in a synthetic effluent. Decolourisation of hydrolysed Reactive Black resulted in an increased toxicity (EC(50) 0.2+/-0.03 mg l(-1)). Toxicity was not detectable when decolourised Reactive Black 5 was metabolised under aerobic conditions. No genotoxicity was detected after the decolourisation of either the parent or the hydrolysed reactive dyes, either in vitro or in the bioreactor. The toxicity and genotoxicity of decolourised C.I. Acid Orange 7 was due to the production of 1-amino-2-naphthol (EC(50) 0.1+/-0.03 mg l(-1)).

A Versatile Route to Unstable Diazo Compounds via Oxadiazolines and their Use in Aryl-Alkyl Cross-Coupling Reactions.

PubMed

Greb, Andreas; Poh, Jian-Siang; Greed, Stephanie; Battilocchio, Claudio; Pasau, Patrick; Blakemore, David C; Ley, Steven V

2017-12-22

Coupling of readily available boronic acids and diazo compounds has emerged recently as a powerful metal-free carbon-carbon bond forming method. However, the difficulty in forming the unstable diazo compound partner in a mild fashion has hitherto limited their general use and the scope of the transformation. Here, we report the application of oxadiazolines as precursors for the generation of an unstable family of diazo compounds using flow UV photolysis and their first use in divergent protodeboronative and oxidative C(sp 2 )-C(sp 3 ) cross-coupling processes, with excellent functional-group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Individual and simultaneous spectrophotometric determination of dapsone and metoclopramide HCl in pharmaceutical dosage forms and synthetic binary mixtures.

PubMed

Omran, Ahmed Ahmed

2005-11-01

A rapid, sensitive and selective spectrophotometric method has been developed for the quantitative determination of dapsone (DAP) and metoclopramide hydrochloride (MCP) in both pure and dosage forms. Individual and simultaneous methods are based on the diazo coupling reaction of these drugs with benzoylacetone (BAC) in alkaline medium. The resulting azo dyes exhibit maximum absorption at 437 and 411 nm with a molar absorptivity of 4.14x10(4) and 2.97x10(4) l mol-1 cm-1 for DAP and MCP, respectively. Simultaneous determination of DAP and MCP was developed utilizing first-order digital derivative spectrophotometry. All variables have been optimized. No interferences were observed from drug excipients and the validity of the methods was tested against reference methods.

Two-photon absorption in diazobenzene compounds

NASA Astrophysics Data System (ADS)

Andrade, A. A.; Yamaki, S. B.; Misoguti, L.; Zilio, S. C.; Atvars, Teresa D. Z.; Oliveira, O. N.; Mendonça, C. R.

2004-12-01

An investigation is made into molecular design strategies to enhance the two-photon absorption (2PA) of organic materials by measuring the 2PA cross-section of diazoaromatic compounds with the femtosecond pulses Z-scan technique at 775 nm. These diazo dyes exhibit a moderate 2PA cross-section, of the order of 300 GM, comparable to those of regular azoaromatic compounds. The increase in the π-electron bridge in the diazoaromatic compounds does not bring, therefore, substantial increase to the measured 2PA intensities, while the main factor to enhance the 2PA cross-section is the presence of charge donor and acceptor groups. It is concluded that current molecular design strategies are unlikely to produce azoaromatic compounds that are useful for applications requiring very high 2PA coefficients.

Solar/UV-induced photocatalytic degradation of three commercial textile dyes.

PubMed

Neppolian, B; Choi, H C; Sakthivel, S; Arabindoo, Banumathi; Murugesan, V

2002-01-28

The photocatalytic degradation of three commercial textile dyes with different structure has been investigated using TiO(2) (Degussa P25) photocatalyst in aqueous solution under solar irradiation. Experiments were conducted to optimise various parameters viz. amount of catalyst, concentration of dye, pH and solar light intensity. Degradation of all the dyes were examined by using chemical oxygen demand (COD) method. The degradation efficiency of the three dyes is as follows: Reactive Yellow 17(RY17) > Reactive Red 2(RR2) > Reactive Blue 4 (RB4), respectively. The experimental results indicate that TiO(2) (Degussa P25) is the best catalyst in comparison with other commercial photocatalysts such as, TiO(2) (Merck), ZnO, ZrO(2), WO(3) and CdS. Though the UV irradiation can efficiently degrade the dyes, naturally abundant solar irradiation is also very effective in the mineralisation of dyes. The comparison between thin-film coating and aqueous slurry method reveals that slurry method is more efficient than coating but the problems of leaching and the requirement of separation can be avoided by using coating technique. These observations indicate that all the three dyes could be degraded completely at different time intervals. Hence, it may be a viable technique for the safe disposal of textile wastewater into the water streams.

Mechanisms and chemistry of dye adsorption on manganese oxides-modified diatomite.

PubMed

Al-Ghouti, Mohammad A; Al-Degs, Yehya S; Khraisheh, Majeda A M; Ahmad, Mohammad N; Allen, Stephen J

2009-08-01

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as delta-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the d-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern.

Kinetics of zero-valent iron reductive transformation of the anthraquinone dye Reactive Blue 4.

PubMed

Epolito, William J; Yang, Hanbae; Bottomley, Lawrence A; Pavlostathis, Spyros G

2008-12-30

The effect of operational conditions and initial dye concentration on the reductive transformation (decolorization) of the textile dye Reactive Blue 4 (RB4) using zero-valent iron (ZVI) filings was evaluated in batch assays. The decolorization rate increased with decreasing pH and increasing temperature, mixing intensity, and addition of salt (100gL(-1) NaCl) and base (3gL(-1) Na2CO3 and 1gL(-1) NaOH), conditions typical of textile reactive dyebaths. ZVI RB4 decolorization kinetics at a single initial dye concentration were evaluated using a pseudo first-order model. Under dyebath conditions and at an initial RB4 concentration of 1000mgL(-1), the pseudo first-order rate constant (kobs) was 0.029+/-0.006h(-1), corresponding to a half-life of 24.2h and a ZVI surface area-normalized rate constant (kSA) of 2.9x10(-4)Lm(-2)h(-1). However, as the initial dye concentration increased, the kobs decreased, suggesting saturation of ZVI surface reactive sites. Non-linear regression of initial decolorization rate values as a function of initial dye concentration, based on a reactive sites saturation model, resulted in a maximum decolorization rate (Vm) of 720+/-88mgL(-1)h(-1) and a half-saturation constant (K) of 1299+/-273mgL(-1). Decolorization of RB4 via a reductive transformation, which was essentially irreversible (2-5% re-oxidation), is believed to be the dominant decolorization mechanism. However, some degree of RB4 irreversible sorption cannot be completely discounted. The results of this study show that ZVI treatment is a promising technology for the decolorization of commercial, anthraquinone-bearing, spent reactive dyebaths.

Fluoride-Mediated Dephosphonylation of α-Diazo-β-carbonyl Phosphonates.

PubMed

Phatake, Ravindra S; Mullapudi, Venkannababu; Wakchaure, Vivek C; Ramana, Chepuri V

2017-01-20

The possibility of fluoride-mediated selective dephosphonylation of α-diazo-β-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting α-diazocarbonyl intermediates undergo a (3 + 2)-cycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess α-diazo-β-carbonyl phosphonates) or Michael addition (with conjugated olefins).

Diazo processing of LANDSAT imagery: A low-cost instructional technique

NASA Technical Reports Server (NTRS)

Lusch, D. P.

1981-01-01

Diazo processing of LANDSAT imagery is a relatively simple and cost effective method of producing enhanced renditions of the visual LANDSAT products. This technique is capable of producing a variety of image enhancements which have value in a teaching laboratory environment. Additionally, with the appropriate equipment, applications research which relys on accurate and repeatable results is possible. Exposure and development equipment options, diazo materials, and enhancement routines are discussed.

Valorization of Waste Obtained from Oil Extraction in Moringa Oleifera Seeds: Coagulation of Reactive Dyes in Textile Effluents.

PubMed

Vilaseca, Mercè; López-Grimau, Víctor; Gutiérrez-Bouzán, Carmen

2014-09-12

Moringa oleifera seeds contain about 40% of highly valued oil due to its wide range of applications, from nutritional issues to cosmetics or biodiesel production. The extraction of Moringa oil generates a waste (65%-75% of seeds weight) which contains a water soluble protein able to be used either in drinking water clarification or wastewater treatment. In this paper, the waste of Moringa oleifera extraction was used as coagulant to remove five reactive dyes from synthetic textile effluents. This waste constitutes a natural coagulant which was demonstrated to be effective for the treatment of industrial reactive dyestuff effluents, characterized by alkaline pH, high NaCl content and hydrolyzed dyes. The coagulation yield increased at high NaCl concentration, whereas the pH did not show any significant effect on dye removal. Moringa oleifera showed better results for dye removal than the conventional treatment of coagulation-flocculation with FeCl₃ and polyelectrolyte. Treated water can be reused in new dyeing processes of cotton fabrics with high quality results.

Valorization of Waste Obtained from Oil Extraction in Moringa Oleifera Seeds: Coagulation of Reactive Dyes in Textile Effluents

PubMed Central

Vilaseca, Mercè; López-Grimau, Víctor; Gutiérrez-Bouzán, Carmen

2014-01-01

Moringa oleifera seeds contain about 40% of highly valued oil due to its wide range of applications, from nutritional issues to cosmetics or biodiesel production. The extraction of Moringa oil generates a waste (65%–75% of seeds weight) which contains a water soluble protein able to be used either in drinking water clarification or wastewater treatment. In this paper, the waste of Moringa oleifera extraction was used as coagulant to remove five reactive dyes from synthetic textile effluents. This waste constitutes a natural coagulant which was demonstrated to be effective for the treatment of industrial reactive dyestuff effluents, characterized by alkaline pH, high NaCl content and hydrolyzed dyes. The coagulation yield increased at high NaCl concentration, whereas the pH did not show any significant effect on dye removal. Moringa oleifera showed better results for dye removal than the conventional treatment of coagulation-flocculation with FeCl3 and polyelectrolyte. Treated water can be reused in new dyeing processes of cotton fabrics with high quality results. PMID:28788199

Comparison of the vanadate oxidase method with the diazo method for serum bilirubin determination in dog, monkey, and rat.

PubMed

Ameri, Mehrdad; Schnaars, Henry; Sibley, John; Honor, David

2011-01-01

The most widely used method for bilirubin concentration determination is the diazo method, which measures the color of azobilirubin. The vanadate oxidase method is based on oxidation of bilirubin to biliverdin by vanadate. The objective of this study was to compare total and direct bilirubin concentration ([Bt] and [Bd], respectively) determined by the diazo and vanadate oxidase methods in pooled serum samples from dogs, monkeys, and rats spiked with panels of different concentrations of bilirubin standards. Pooled serum samples from 40 dogs, 40 monkeys, and 60 rats were spiked with either ditaurine conjugates of bilirubin or a standard reference material. The results obtained from both assays were compared using Deming regression analysis. The intra- and interassay precision, expressed as a percentage of the coefficient of variation (%CV), was determined for [Bt] and [Bd], and the mean percentage of recovery was calculated. The vanadate oxidase method displayed an excellent correlation (r  =  0.99-1.00) with the diazo method. Using Deming regression, there were minimal negative or positive constant and proportional biases for [Bt] and [Bd]. The precision studies revealed that the vanadate oxidase method has comparable between-run and within-run CVs to those of the diazo method. The recovery study demonstrated that the diazo method more closely approximates the expected values of [Bt]. In conclusion, the vanadate oxidase method is a simple and rapid method that can be employed as an alternative to the diazo method when interfering substances are present in the serum samples of dog, monkey, and rat.

IDENTIFICATION OF REACTIVE DYES IN SPENT DYEBATHS AND WASTEWATER BY CAPILLARY ELECTROPHORESIS/MASS SPECTROMETRY

EPA Science Inventory

Capillary electrophoresis with diode array detection and mass spectrometry combined with solid-phase extraction were employed for the identification of reactive vinylsulfone and chlorotriazine dyes and their hydrolysis products in spent dyebaths and raw and treated wastewater. Re...

Decolorization of industrial synthetic dyes using engineered Pseudomonas putida cells with surface-immobilized bacterial laccase

PubMed Central

2012-01-01

Background Microbial laccases are highly useful in textile effluent dye biodegradation. However, the bioavailability of cellularly expressed or purified laccases in continuous operations is usually limited by mass transfer impediment or enzyme regeneration difficulty. Therefore, this study develops a regenerable bacterial surface-displaying system for industrial synthetic dye decolorization, and evaluates its effects on independent and continuous operations. Results A bacterial laccase (WlacD) was engineered onto the cell surface of the solvent-tolerant bacterium Pseudomonas putida to construct a whole-cell biocatalyst. Ice nucleation protein (InaQ) anchor was employed, and the ability of 1 to 3 tandemly aligned N-terminal repeats to direct WlacD display were compared. Immobilized WlacD was determined to be surface-displayed in functional form using Western blot analysis, immunofluorescence microscopy, flow cytometry, and whole-cell enzymatic activity assay. Engineered P. putida cells were then applied to decolorize the anthraquinone dye Acid Green (AG) 25 and diazo-dye Acid Red (AR) 18. The results showed that decolorization of both dyes is Cu2+- and mediator-independent, with an optimum temperature of 35°C and pH of 3.0, and can be stably performed across a temperature range of 15°C to 45°C. A high activity toward AG25 (1 g/l) with relative decolorization values of 91.2% (3 h) and 97.1% (18 h), as well as high activity to AR18 (1 g/l) by 80.5% (3 h) and 89.0% (18 h), was recorded. The engineered system exhibited a comparably high activity compared with those of separate dyes in a continuous three-round shake-flask decolorization of AG25/AR18 mixed dye (each 1 g/l). No significant decline in decolorization efficacy was noted during first two-rounds but reaction equilibriums were elongated, and the residual laccase activity eventually decreased to low levels. However, the decolorizing capacity of the system was easily retrieved via a subsequent 4-h cell culturing. Conclusions This study demonstrates, for the first time, the methodology by which the engineered P. putida with surface-immobilized laccase was successfully used as regenerable biocatalyst for biodegrading synthetic dyes, thereby opening new perspectives in the use of biocatalysis in industrial dye biotreatment. PMID:22686507

Thermodynamic and Spectroscopic Investigation of Interactions between Reactive Red 223 and Reactive Orange 122 Anionic Dyes and Cetyltrimethyl Ammonium Bromide (CTAB) Cationic Surfactant in Aqueous Solution

PubMed Central

Irfan, Muhammad; Usman, Muhammad; Mansha, Asim; Rasool, Nasir; Ibrahim, Muhammad; Rana, Usman Ali; Siddiq, Mohammad; Zia-Ul-Haq, Muhammad; Jaafar, Hawa Z. E.; Khan, Salah Ud-Din

2014-01-01

The present study describes the conductometric and spectroscopic study of the interaction of reactive anionic dyes, namely, reactive red 223 and reactive orange 122 with the cationic surfactant cetyltrimethyl ammonium bromide (CTAB). In a systematic investigation, the electrical conductivity data was used to calculate various thermodynamic parameters such as free energy (ΔG), enthalpy (ΔH), and the entropy (ΔS) of solubilization. The trend of change in these thermodynamic quantities indicates toward the entropy driven solubilization process. Moreover, the results from spectroscopic data reveal high degree of solubilization, with strong interactions observed in the cases of both dyes and the CTAB. The spontaneous nature of solubilization and binding was evident from the observed negative values of free energies (ΔG p and ΔG b). PMID:25243216

A Coupling of Benzamides and Donor/Acceptor Diazo–Compounds to form γ-Lactams via Rh(III)–Catalyzed C–H Activation

PubMed Central

Hyster, Todd K.; Ruhl, Kyle E.; Rovis, Tomislav

2013-01-01

The coupling of O-pivaloyl benzhydroxamic acids with donor/acceptor diazo compounds provides iso-indolones in high yield. The reaction tolerates a broad range of benzhydroxamic acids and diazo compounds including substituted 2,2,2-trifluorodiazo ethanes. Mechanistic experiments suggest that C–H activation is turnover limiting and irreversible, while insertion of the diazo compound favors electron deficient substrates. PMID:23548055

Crystal structure of 2-diazo-imidazole-4,5-dicarbo-nitrile.

PubMed

Parrish, Damon A; Kramer, Stephanie; Windler, G Kenneth; Chavez, David E; Leonard, Philip W

2015-07-01

In the title compound, C5N6, all the atoms are approximately coplanar. In the crystal, mol-ecules are packed with short contact distances of 2.885 (2) (between the diazo N atom connected to the ring and a cyano N atom on a neighboring mol-ecule) and 3.012 (2) Å (between the terminal diazo N atom and an N atom of a neighboring imidazole ring).

Geminal difunctionalization of α-diazo arylmethylphosphonates: synthesis of fluorinated phosphonates.

PubMed

Zhou, Yujing; Zhang, Yan; Wang, Jianbo

2016-11-08

A general approach towards diverse fluorinated phosphonates via geminal difunctionalization reactions of α-diazo arylmethylphosphonates is described. The diazo functionality (RR'C[double bond, length as m-dash]N 2 ) is successfully converted to RR'CF 2 , RR'CHF, RR'CFBr or RR'CFNR'' 2 groups by employing different fluorination reagents. A variety of fluorinated organophosphorus compounds were readily accessed in good to excellent yields from a common type of precursor.

A reagent for safe and efficient diazo-transfer to primary amines: 2-azido-1,3-dimethylimidazolinium hexafluorophosphate.

PubMed

Kitamura, Mitsuru; Kato, So; Yano, Masakazu; Tashiro, Norifumi; Shiratake, Yuichiro; Sando, Mitsuyoshi; Okauchi, Tatsuo

2014-07-07

Organic azides were prepared from primary amines in high yields by a metal free diazo-transfer reaction using 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP), which is safe and stable crystalline. The choice of base was important in the diazo-transfer reaction. In general, 4-(N,N-dimethyl)aminopyridine (DMAP) was efficient, but a stronger base such as alkylamine or DBU was more appropriate for the reaction of nucleophilic primary amines. X-ray single crystal structural analysis and geometry optimization using density functional theory (B3LYP/6-31G**) were conducted to study the ADMP structure, and the diazo-transfer reaction mechanism was explained with the help of the results of these analyses.

Diazo compounds in continuous-flow technology.

PubMed

Müller, Simon T R; Wirth, Thomas

2015-01-01

Diazo compounds are very versatile reagents in organic chemistry and meet the challenge of selective assembly of structurally complex molecules. Their leaving group is dinitrogen; therefore, they are very clean and atom-efficient reagents. However, diazo compounds are potentially explosive and extremely difficult to handle on an industrial scale. In this review, it is discussed how continuous flow technology can help to make these powerful reagents accessible on large scale. Microstructured devices can improve heat transfer greatly and help with the handling of dangerous reagents safely. The in situ formation and subsequent consumption of diazo compounds are discussed along with advances in handling diazomethane and ethyl diazoacetate. The potential large-scale applications of a given methodology is emphasized. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO2) and adsorption of remazol reactive dye

NASA Astrophysics Data System (ADS)

Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

2015-09-01

Nanoporous amorphous-MnO2 was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH3COO)2.4H2O) in 0.1 M KMnO4. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO2 bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO2. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye on 0.2g synthesized nanoporous amorphous-MnO2 showed 99 - 100% decolorization.

The collagen type I segment long spacing (SLS) and fibrillar forms: Formation by ATP and sulphonated diazo dyes.

PubMed

Harris, J Robin; Lewis, Richard J

2016-07-01

The collagen type I segment long spacing (SLS) crystallite is a well-ordered rod-like molecular aggregate, ∼300nm in length, which is produced in vitro under mildly acidic conditions (pH 2.5-3.5) in the presence of 1mM ATP. The formation of the SLS crystallite amplifies the inherent linear structural features of individual collagen heterotrimers, due to the punctate linear distribution and summation of the bulkier amino acid side chains along the length of individual collagen heterotrimers. This can be correlated structurally with the 67nm D-banded collagen fibril that is found in vivo, and formed in vitro. Although first described many years ago, the range of conditions required for ATP-induced SLS crystallite formation from acid-soluble collagen have not been explored extensively. Consequently, we have addressed biochemical parameters such as the ATP concentration, pH, speed of formation and stability so as to provide a more complete structural understanding of the SLS crystallite. Treatment of collagen type I with 1mM ATP at neutral and higher pH (6.0-9.0) also induced the formation of D-banded fibrils. Contrary to previous studies, we have shown that the polysulphonated diazo dyes Direct red (Sirius red) and Evans blue, but not Congo red and Methyl blue, can also induce the formation of SLS-like aggregates of collagen, but under markedly different ionic conditions to those employed in the presence of ATP. Specifically, pre-formed D-banded collagen fibrils, prepared in a higher than the usual physiological NaCl concentration (e.g. 500mM NaCl, 20mM Tris-HCl pH7.4 or x3 PBS), readily form SLS aggregates when treated with 0.1mM Direct red and Evans blue, but this did not occur at lower NaCl concentrations. These new data are discussed in relation to the anion (Cl(-)) and polyanion (phosphate and sulphonate) binding by the collagen heterotrimer and their likely role in collagen fibrillogenesis and SLS formation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Combined use of UV-labile calcium chelators and calcium-sensitive dyes in a microscope with two light sources influencing different regions in a group of coordinated contracting cardiac myocytes

NASA Astrophysics Data System (ADS)

Pilarczyk, Goetz; Greulich, Karl-Otto

1997-12-01

The coordination of excitation in a biological system of cells such as cardiac myocytes in heart tissue has crucial influence on the function of the entire organ. This coordinated behavior can be visualized in a small group of embryonic cardiac myocytes derived from the hearts of unborn chicken. Loaded with a calcium sensitive dye the excitation can be imaged via the occurring transient rise in cytosolic calcium concentration. It can be shown that in regions with physiological or morphological restrictions the transient rise in cytosolic calcium occurs with a temporal delay compared to the ordinary array of coupled myocytes. The height of the transient rise of cytosolic calcium is related to the ability of the individual cell to participate in the coordinated contraction. The free cytosolic calcium concentration is decreased with the UV-labile calcium, chelator diazo-2. Our setup allows to decrease the free cytosolic calcium in a single cell of the contracting array of cells. This allows us to introduce mismatches in selected regions of the coordinated contraction and to visualize the effects simultaneously.

Iron-catalyzed intermolecular cycloaddition of diazo surrogates with hexahydro-1,3,5-triazines.

PubMed

Liu, Pei; Zhu, Chenghao; Xu, Guangyang; Sun, Jiangtao

2017-09-26

We report here an unprecedented iron-catalyzed cycloaddition reaction of diazo surrogates with hexahydro-1,3,5-triazines, providing five-membered heterocycles in moderate to high yields under mild reaction conditions. This cycloaddition features C-N and C-C bond formation using a cheap iron catalyst. Importantly, different to our former report on a gold-catalyzed system, both donor/donor and donor/acceptor diazo substrates are tolerated in this iron-catalyzed protocol.

Synthesis of Donor/Acceptor-Substituted Diazo Compounds in Flow and Their Application in Enantioselective Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.

PubMed

Rackl, Daniel; Yoo, Chun-Jae; Jones, Christopher W; Davies, Huw M L

2017-06-16

A tandem reaction system has been developed for the preparation of donor/acceptor-substituted diazo compounds in continuous flow coupled to dirhodium-catalyzed C-H functionalization or cyclopropanation. Hydrazones were oxidized in flow by solid-supported N-iodo-p-toluenesulfonamide potassium salt (PS-SO 2 NIK) to generate the diazo compounds, which were then purified by passing through a column of molecular sieves/sodium thiosulfate.

Solid waste from leather industry as adsorbent of organic dyes in aqueous-medium.

PubMed

Oliveira, Luiz C A; Gonçalves, Maraísa; Oliveira, Diana Q L; Guerreiro, Mário C; Guilherme, Luiz R G; Dallago, Rogério M

2007-03-06

The industrial tanning of leather usually produces considerable amounts of chromium-containing solid waste and liquid effluents and raises many concerns on its environmental effect as well as on escalating landfill costs. Actually, these shortcomings are becoming increasingly a limiting factor to this industrial activity that claims for alternative methods of residue disposals. In this work, it is proposed a novel alternative destination of the solid waste, based on the removal of organic contaminants from the out coming aqueous-residue. The adsorption isotherm pattern for the wet blue leather from the Aurea tanning industry in Erechim-RS (Brazil) showed that these materials present high activity on adsorbing the reactive red textile dye as well as other compounds. The adsorbent materials were characterized by IR spectroscopy and SEM and tested for the dye adsorption (reactive textile and methylene blue dyes). The concentrations of dyes were measured by UV-vis spectrophotometry and the chromium extraction from leather waste was realized by basic hydrolysis and determined by atomic absorption. As a low cost abundant adsorbent material with high adsorption ability on removing dye methylene blue (80mgg(-1)) and textile dye reactive red (163mgg(-1)), the leather waste is revealed to be a interesting alternative relatively to more costly adsorbent materials.

Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents.

PubMed

Hari, Durga Prasad; Waser, Jerome

2016-02-24

Alkynes have found widespread applications in synthetic chemistry, biology, and materials sciences. In recent years, methods based on electrophilic alkynylation with hypervalent iodine reagents have made acetylene synthesis more flexible and efficient, but they lead to the formation of one equivalent of an iodoarene as side-product. Herein, a more efficient strategy involving a copper-catalyzed oxy-alkynylation of diazo compounds with ethynylbenziodoxol(on)e (EBX) reagents is described, which proceeds with generation of nitrogen gas as the only waste. This reaction is remarkable for its broad scope in both EBX reagents and diazo compounds. In addition, vinyl diazo compounds gave enynes selectively as single geometric isomers. The functional groups introduced during the transformation served as easy handles to access useful building blocks for synthetic and medicinal chemistry.

Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO{sub 2}) and adsorption of remazol reactive dye

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali, E-mail: rozali@ukm.edu.my

2015-09-25

Nanoporous amorphous-MnO{sub 2} was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH{sub 3}COO){sub 2}.4H{sub 2}O) in 0.1 M KMnO{sub 4}. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO{sub 2} bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO{sub 2}. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye onmore » 0.2g synthesized nanoporous amorphous-MnO{sub 2} showed 99 – 100% decolorization.« less

Enantioselective Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds.

PubMed

Hari, Durga Prasad; Waser, Jerome

2017-06-28

Enantioselective catalytic methods allowing the addition of both a nucleophile and an electrophile onto diazo compounds give a fast access into important building blocks. Herein, we report the highly enantioselective oxyalkynylation of diazo compounds using ethynylbenziodoxol-(on)e reagents and a simple copper bisoxazoline catalyst. The obtained α-benzoyloxy propargylic esters are useful building blocks, which are difficult to synthesize in enantiopure form using other methods. The obtained products could be efficiently transformed into vicinal diols and α-hydroxy propargylic esters without loss in enantiopurity.

Synthesis of spiro-4H-pyrazole-oxindoles and fused 1H-pyrazoles via divergent, thermally induced tandem cyclization/migration of alkyne-tethered diazo compounds.

PubMed

Zhang, Cheng; Dong, Shanliang; Zheng, Yang; He, Ciwang; Chen, Jiaolong; Zhen, Jingsen; Qiu, Lihua; Xu, Xinfang

2018-01-31

A thermally induced, substrate-dependent reaction of alkynyl diazo compounds has been developed. This transformation produces spiro-4H-pyrazole-oxindoles and fused 1H-pyrazoles in good to high yields from the corresponding alpha-cyano and alpha-sulfonyl diazo compounds. The salient features of this reaction include excellent chemoselectivity and atom-economy, mild reaction conditions, simple purification and potential for large scale production.

Gold(I)-catalyzed diazo cross-coupling: a selective and ligand-controlled denitrogenation/cyclization cascade.

PubMed

Xu, Guangyang; Zhu, Chenghao; Gu, Weijin; Li, Jian; Sun, Jiangtao

2015-01-12

An unprecedented gold-catalyzed ligand-controlled cross-coupling of diazo compounds by sequential selective denitrogenation and cyclization affords N-substituted pyrazoles in a position-switchable mode. This novel transformation features selective decomposition of one diazo moiety and simultaneous preservation of the other one from two substrates. Notably, the choice of the ancillary ligand to the gold complex plays a pivotal role on the chemo- and regioselectivity of the reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo Compounds: Formation of Olefins from Two Different Carbene Precursors.

PubMed

Wang, Bo; Yi, Heng; Zhang, Hang; Sun, Tong; Zhang, Yan; Wang, Jianbo

2018-01-19

Formal carbene dimerization is a convergent method for the synthesis of alkenes. Herein, we report a Ru(II)-catalyzed carbene dimerization of cyclopropenes and diazo compounds. The yields are up to 97% and the stereoselectivity are up to >20:1. Mechanistically, it has been experimentally demonstrated that the catalyst reacts with cyclopropene first to generate a Ru(II)-carbene species, which is attacked by nucleophilic diazo substrate, followed by dinitrogen extrusion to form the double bond.

Synthesis of Imidazopyridines via Copper-Catalyzed, Formal Aza-[3 + 2] Cycloaddition Reaction of Pyridine Derivatives with α-Diazo Oxime Ethers.

PubMed

Park, Sangjune; Kim, Hyunseok; Son, Jeong-Yu; Um, Kyusik; Lee, Sooho; Baek, Yonghyeon; Seo, Boram; Lee, Phil Ho

2017-10-06

The Cu-catalyzed, formal aza-[3 + 2] cycloaddition reaction of pyridine derivatives with α-diazo oxime ethers in trifluoroethanol was used to synthesize imidazopyridines via the release of molecular nitrogen and elimination of alcohol. These methods enabled modular synthesis of a wide range of N-heterobicyclic compounds such as imidazopyridazines, imidazopyrimidines, and imidazopyrazines with an α-imino Cu-carbenoid generated from the α-diazo oxime ethers and copper.

Characterization of tannery sludge activated carbon and its utilization in the removal of azo reactive dye.

PubMed

Geethakarthi, A; Phanikumar, B R

2012-03-01

The removal of azo Reactive Red 31(RR31) from synthetic dye solution using tannery sludge-developed activated carbon (TSC) was investigated. TSC was prepared from a combination of physical and chemical activation. The developed TSC was characterized by FT-IR, SEM, TG-DTA, specific surface area and zero point charge of pH (pH(zpc)). The isotherm models, kinetic models and thermodynamic parameters were also analysed to describe the adsorptive behaviour of TSC. The effect of contact time, initial dye concentration, carbon dosage, agitation speed, initial pH and temperature were carried out for batch adsorption studies. The isotherm plot of the dye RR31 on TSC fitted better with the Langmuir adsorption isotherm than the Freundlich model. The maximum monolayer adsorption capacity of TSC in the removal of RR31 ranged from 23.15 to 39.37 mg/g. The thermodynamic parameters showed the endothermic and physical nature of the Reactive Red 31 adsorption on TSC. The entropy and enthalpy values were 181.515 J/Kmol and 5.285 kJ/mol, respectively. The developed cationic tannery sludge carbon was found to be an effective adsorbent in the removal of the anionic azo reactive dye RR31.

Assessment of the banana pseudostem as a low-cost biosorbent for the removal of reactive blue 5G dye.

PubMed

Módenes, Aparecido N; Espinoza-Quiñones, Fernando R; Geraldi, Claudinéia A Q; Manenti, Diego R; Trigueros, Daniela E G; Oliveira, Ana Paula de; Borba, Carlos E; Kroumov, Alexander D

2015-01-01

In this work, the removal of reactive blue 5G (RB5G) dye using the drying biomass of banana pseudostem (BPS) was investigated. The characterization of BPS particles was performed. Improvement in the RB5G dye removal performance at the following sorption conditions was evidenced: pH 1, 30°C sorption temperature and 40 rpm shaking, regardless of the particle size range. Kinetic RB5G dye sorption data obtained at better conditions fit well in an Elovich model. A combined Langmuir-BET isotherm model provides a good representation of the RB5G dye equilibrium sorption data, which shows the evidence of a physical sorption process on the BPS surface. Based on the results, the removal of RB5G dye molecules by BPS is based on a physical sorption process.

Structural Insights into 2,2′-Azino-Bis(3-Ethylbenzothiazoline-6-Sulfonic Acid) (ABTS)-Mediated Degradation of Reactive Blue 21 by Engineered Cyathus bulleri Laccase and Characterization of Degradation Products

PubMed Central

Kenzom, T.; Srivastava, P.

2014-01-01

Advanced oxidation processes are currently used for the treatment of different reactive dyes which involve use of toxic catalysts. Peroxidases are reported to be effective on such dyes and require hydrogen peroxide and/or metal ions. Cyathus bulleri laccase, expressed in Pichia pastoris, catalyzes efficient degradation (78 to 85%) of reactive azo dyes (reactive black 5, reactive orange 16, and reactive red 198) in the presence of synthetic mediator ABTS [2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)]. This laccase was engineered to degrade effectively reactive blue 21 (RB21), a phthalocyanine dye reported to be decolorized only by peroxidases. The 816-bp segment (toward the C terminus) of the lcc gene was subjected to random mutagenesis and enzyme variants (Lcc35, Lcc61, and Lcc62) were selected based on increased ABTS oxidizing ability. Around 78 to 95% decolorization of RB21 was observed with the ABTS-supplemented Lcc variants in 30 min. Analysis of the degradation products by mass spectrometry indicated the formation of several low-molecular-weight compounds. Mapping the mutations on the modeled structure implicated residues both near and far from the T1 Cu site that affected the catalytic efficiency of the mutant enzymes on ABTS and, in turn, the rate of oxidation of RB21. Several inactive clones were also mapped. The importance of geometry as well as electronic changes on the reactivity of laccases was indicated. PMID:25261507

Structural insights into 2,2'-azino-Bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS)-mediated degradation of reactive blue 21 by engineered Cyathus bulleri Laccase and characterization of degradation products.

PubMed

Kenzom, T; Srivastava, P; Mishra, S

2014-12-01

Advanced oxidation processes are currently used for the treatment of different reactive dyes which involve use of toxic catalysts. Peroxidases are reported to be effective on such dyes and require hydrogen peroxide and/or metal ions. Cyathus bulleri laccase, expressed in Pichia pastoris, catalyzes efficient degradation (78 to 85%) of reactive azo dyes (reactive black 5, reactive orange 16, and reactive red 198) in the presence of synthetic mediator ABTS [2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)]. This laccase was engineered to degrade effectively reactive blue 21 (RB21), a phthalocyanine dye reported to be decolorized only by peroxidases. The 816-bp segment (toward the C terminus) of the lcc gene was subjected to random mutagenesis and enzyme variants (Lcc35, Lcc61, and Lcc62) were selected based on increased ABTS oxidizing ability. Around 78 to 95% decolorization of RB21 was observed with the ABTS-supplemented Lcc variants in 30 min. Analysis of the degradation products by mass spectrometry indicated the formation of several low-molecular-weight compounds. Mapping the mutations on the modeled structure implicated residues both near and far from the T1 Cu site that affected the catalytic efficiency of the mutant enzymes on ABTS and, in turn, the rate of oxidation of RB21. Several inactive clones were also mapped. The importance of geometry as well as electronic changes on the reactivity of laccases was indicated. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Solar light induced and TiO2 assisted degradation of textile dye reactive blue 4.

PubMed

Neppolian, B; Choi, H C; Sakthivel, S; Arabindoo, B; Murugesan, V

2002-03-01

Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A solution containing 4 x 10(-4) M dye was completely degraded in 24 h irradiation time. The intensity of the solar light was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2, SO4(2-), NO3-, NH4+ and H2O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate influenced the photodegradation efficiency. The rapidity of photodegradation of dye intermediates were observed in the presence of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride substantially affected the photodegradation efficiency. High performance liquid chromatography and chemical oxygen demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light induced degradation of textile dye in wastewater is a viable technique for wastewater treatment.

Catalyst-Dependent Chemoselective Formal Insertion of Diazo Compounds into C-C or C-H Bonds of 1,3-Dicarbonyl Compounds.

PubMed

Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A; Bi, Xihe

2018-05-08

A catalyst-dependent chemoselective one-carbon insertion of diazo compounds into the C-C or C-H bonds of 1,3-dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)-C bond of the 1,3-dicarbonyl substrate leads to a 1,4-dicarbonyl product containing an all-carbon α-quaternary center. This reaction constitutes the first example of an insertion of diazo-derived carbenoids into acyclic C-C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C-H insertion, affording 2-alkylated 1,3-dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst-dependent chemoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies of a Diazo Cyclopropanation Strategy for the Total Synthesis of (-)-Lundurine A.

PubMed

Huang, Hong-Xiu; Jin, Shuai-Jiang; Gong, Jin; Zhang, Dan; Song, Hao; Qin, Yong

2015-09-14

The bioactive Kopsia alkaloids lundurines A-D are the only natural products known to contain indolylcyclopropane. Achieving their syntheses can provide important insights into their biogenesis, as well as novel synthetic routes for complex natural products. Asymmetric total synthesis of (-)-lundurine A has previously been achieved through a Simmons-Smith cyclopropanation strategy. Here, the total synthesis of (-)-lundurine A was carried out using a metal-catalyzed diazo cyclopropanation strategy. In order to avoid a carbene CH insertion side reaction during cyclopropanation of α-diazo- carboxylates or cyanides, a one-pot, copper-catalyzed Bamford-Stevens diazotization/diazo decomposition/cyclopropanation cascade was developed, involving hydrazone. This approach simultaneously generates the C/D/E ring system and the two chiral quaternary centers at C2 and C7. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of biological decolorisation of anthraquinone based Reactive Blue 19 using an isolated strain of Enterobacter sp.F NCIM 5545.

PubMed

Holkar, Chandrakant R; Pandit, Aniruddha B; Pinjari, Dipak V

2014-12-01

In the present study, an attempt was made to evaluate the bacterial decolorisation of Reactive Blue 19 by an Enterobacter sp.F which was isolated from a mixed culture from anaerobic digester for biogas production. Phenotypic characterization and phylogenetic analysis based on DNA sequencing comparisons indicate that Enterobacter sp.F was 99.7% similar to Enterobacter cloacae ATCC13047. The kinetics of Reactive Blue 19 dye decolorisation by bacterium had been estimated. Effects of substrate concentration, oxygen, temperature, pH, glucose and glucose to microbe weight ratio on the rate of decolorisation were investigated to understand key factor that determines the performance of dye decolorisation. The maximum decolorisation efficiency of Reactive Blue 19 was 90% over period of 24 h for optimized parameter. To the best of our knowledge, this research study is the report where Enterobacter sp.F has been reported with about 90% decolorizing ability against anthraquinone based Reactive Blue 19 dye. Copyright © 2014 Elsevier Ltd. All rights reserved.

A study of Reactive Red 198 adsorption on iron filings from aqueous solutions.

PubMed

Azhdarpoor, Abooalfazl; Nikmanesh, Roya; Khademi, Fahime

2014-01-01

In recent years, reactive dyes have been widely used in textile industries with particular efficiency. They dyes are often toxic, carcinogenic and mutagenic. Improper treatment and non-scientific disposal of dyed wastewater from these industries into water sources has created many environmental problems and concerns around the world. The purpose of the present study is to investigate the efficiency of iron filings in adsorption of Reactive Red 198 from aqueous solutions. This study was conducted using an experimental method at the laboratory scale. In this study, the effects of operating parameters such as pH (1-11), initial dye concentration (40-400 mg/L), contact time (5-120 min) and iron dose (0.1-1 g) with a mesh of<100 were studied. Dye concentration was determined using a spectrophotometer at a wavelength of 520 nm. The results indicated that maximum adsorption capacity of the dye in question was obtained at pH 3, contact time of 60 min and adsorbent dose of 1 g. At initial dye concentration of 100 and 200 mg/L, by increasing the dose of waste iron from 0.1 to 1 g, the removal percentage increased from approximately 76.89% to 97.28% and from 22.64% to 68.03%, respectively. At pH 3, contact time of 5 min and constant waste iron dose of 0.8 g, the dye removal efficiency was 85.34%. By increasing the contact time to 120 min, the removal efficiency increased to 99.2%. Welding iron waste as an inexpensive and available adsorbent has an optimum ability for adsorption of Reactive Red 198 from aqueous solutions.

Effect of light on the kinetics and equilibrium of the textile dye (Reactive Red 120) adsorption by Helianthus annuus hairy roots.

PubMed

Srikantan, Chitra; Suraishkumar, G K; Srivastava, Smita

2018-06-01

The study demonstrates for the first time that light influences the adsorption equilibrium and kinetics of a dye by root culture system. The azo dye (Reactive Red 120) adsorption by the hairy roots of H. annuus followed a pseudo first-order kinetic model and the adsorption equilibrium parameters were best estimated using Langmuir isotherm. The maximum dye adsorption capacity of the roots increased 6-fold, from 0.26 mg g -1 under complete dark conditions to 1.51 mg g -1 under 16/8 h light/dark photoperiod. Similarly, adsorption rate of the dye and removal (%) also increased in the presence of light, irrespective of the initial concentration of the dye (20-110 mg L -1 ). The degradation of the azo dye upon adsorption by the hairy roots of H. annuus was also confirmed. In addition, a strategy for simultaneous dye removal and increased alpha-tocopherol (industrially relevant) production by H. annuus hairy root cultures has been proposed and demonstrated. Copyright © 2018 Elsevier Ltd. All rights reserved.

Silver-Catalyzed Cyclopropanation of Alkenes Using N-Nosylhydrazones as Diazo Surrogates.

PubMed

Liu, Zhaohong; Zhang, Xinyu; Zanoni, Giuseppe; Bi, Xihe

2017-12-15

An efficient silver-catalyzed [2 + 1] cyclopropanation of sterically hindered internal alkenes with diazo compounds in which room-temperature-decomposable N-nosylhydrazones are used as diazo surrogates is reported. The unexpected unique catalytic activity of silver was ascribed to its dual role as a Lewis acid activating alkene substrates and as a transition metal forming silver carbenoids. A wide range of internal alkenes, including challenging diarylethenes, were suitable for this protocol, thereby affording a variety of cyclopropanes with high efficiency in a stereoselective manner under mild conditions.

Decolorization of acid, disperse and reactive dyes by Trametes versicolor CBR43.

PubMed

Yang, Seung-Ok; Sodaneath, Hong; Lee, Jung-In; Jung, Hyekyeng; Choi, Jin-Hee; Ryu, Hee Wook; Cho, Kyung-Suk

2017-07-29

The mycoremediation has been considered as a promising method for decolorizing dye wastewater. To explore new bioresource for mycoremediation, a new white-rot fungus that could decolorize various dyes commonly used in textile industries was isolated, and its ligninolytic enzyme activity and decolorization capacity were characterized. The isolated CBR43 was identified as Trametes versicolor based on the morphological properties of its fruit body and spores, as well as through partial 18S rDNA gene sequences. Isolated CBR43 displayed high activities of laccase and Mn-dependent peroxidase, whereas its lignin peroxidase activity was relatively low. These ligninolytic enzyme activities in potato dextrose broth (PDB) medium were enhanced by the addition of yeast extract (1-10 g L -1 ). In particular, lignin peroxidase activity was increased more than 5 times in the PDB medium amended with 10 g L -1 of yeast extract. The CBR43 decolorized more than 90% of 200 mg L -1 acid dyes (red 114, blue 62 and black 172) and reactive dyes (red 120, blue 4, orange 16 and black 5) within 6 days in the PDB medium. CBR43 decolorized 67% of 200 mg L -1 acid orange 7 within 9 days. The decolorization efficiencies for disperse dyes (red 1, orange 3 and black 1) were 51-80% within 9 days. The CBR43 could effectively decolorize high concentrations of acid blue 62 and acid black 172 (500-700 mg L -1 ). The maximum dye decolorization rate was obtained at 28°C, pH 5, and 150 rpm in the PDB medium. T. versicolor CBR43 had high laccase and Mn-dependent peroxidase activities, and could decolorize a wide variety of dyes such as acid, disperse and reactive textile dyes. This fungus had decolorizing activities of azo-type dyes as well as anthraquinone-type dyes. T. versicolor CBR43 is one of promising bioresources for the decolorization of textile wastewater including various dyes.

Pad ultrasonic batch dyeing of causticized lyocell fabric with reactive dyes.

PubMed

Babar, Aijaz Ahmed; Peerzada, Mazhar Hussain; Jhatial, Abdul Khalique; Bughio, Noor-Ul-Ain

2017-01-01

Conventionally, cellulosic fabric dyed with reactive dyes requires significant amount of salt. However, the dyeing of a solvent spun regenerated cellulosic fiber is a critical process. This paper presents the dyeing results of lyocell fabrics dyed with conventional pad batch (CPB) and pad ultrasonic batch (PUB) processes. The dyeing of lyocell fabrics was carried out with two commercial dyes namely Drimarine Blue CL-BR and Ramazol Blue RGB. Dyeing parameters including concentration of sodium hydroxide, sodium carbonate and dwell time were compared for the two processes. The outcomes show that PUB dyed samples offered reasonably higher color yield and dye fixation than CPB dyed samples. A remarkable reduction of 12h in batching time, 18ml/l in NaOH and 05g/l in Na 2 CO 3 quantity was observed for PUB processed samples producing similar results compared to CPB process, making PUB a more economical, productive and an environment friendly process. Color fastness examination witnessed identical results for both PUB and CPB methods. No significant change in surface morphology of PUB processed samples was observed through scanning electron microscope (SEM) analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Asymmetric Catalysis with Organic Azides and Diazo Compounds Initiated by Photoinduced Electron Transfer.

PubMed

Huang, Xiaoqiang; Webster, Richard D; Harms, Klaus; Meggers, Eric

2016-09-28

Electron-acceptor-substituted aryl azides and α-diazo carboxylic esters are used as substrates for visible-light-activated asymmetric α-amination and α-alkylation, respectively, of 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium-based Lewis acid in combination with a photoredox sensitizer. This novel proton- and redox-neutral method provides yields of up to 99% and excellent enantioselectivities of up to >99% ee with broad functional group compatibility. Mechanistic investigations suggest that an intermediate rhodium enolate complex acts as a reductive quencher to initiate a radical process with the aryl azides and α-diazo carboxylic esters serving as precursors for nitrogen and carbon-centered radicals, respectively. This is the first report on using aryl azides and α-diazo carboxylic esters as substrates for asymmetric catalysis under photoredox conditions. These reagents have the advantage that molecular nitrogen is the leaving group and sole byproduct in this reaction.

Isolation and Characterization of Paracoccus sp. GSM2 Capable of Degrading Textile Azo Dye Reactive Violet 5

PubMed Central

Bheemaraddi, Mallikarjun C.; Shivannavar, Channappa T.; Gaddad, Subhashchandra M.

2014-01-01

A potential bacterial strain GSM2, capable of degrading an azo dye Reactive Violet 5 as a sole source of carbon, was isolated from textile mill effluent from Solapur, India. The 16S rDNA sequence and phenotypic characteristics indicated an isolated organism as Paracoccus sp. GSM2. This strain exhibited complete decolorization of Reactive Violet 5 (100 mg/L) within 16 h, while maximally it could decolorize 800 mg/L of dye within 38 h with 73% decolorization under static condition. For color removal, the most suitable pH and temperature were pH 6.0–9.0 and 25–40°C, respectively. The isolate was able to decolorize more than 70% of five structurally different azo dyes within 38 h. The isolate is salt tolerant as it can bring out more than 90% decolorization up to a salt concentration of 2% (w/v). UV-Visible absorption spectra before and after decolorization suggested that decolorization was due to biodegradation and was further confirmed by FT-IR spectroscopy. Overall results indicate the effectiveness of the strain GSM2 explored for the treatment of textile industry effluents containing various azo dyes. To our knowledge, this could be the first report on biodegradation of Reactive Violet 5 by Paracoccus sp. GSM2. PMID:24883397

Bioanalysis of 6-Diazo-5-oxo-L-norleucine (DON) in plasma and brain by ultra-performance liquid chromatography mass spectrometry

PubMed Central

Alt, Jesse; Potter, Michelle C.; Rojas, Camilo; Slusher, Barbara S.

2015-01-01

Glutamine is an abundant amino acid that plays pivotal roles in cell growth, cell metabolism and neurotransmission. Dysregulation of glutamine-utilizing pathways has been associated with pathological conditions such as cancer and neurodegenerative diseases. 6-Diazo-5-Oxo-L-Norleucine (DON) is a reactive glutamine analog that inhibits enzymes affecting glutamine metabolism such as glutaminase, 2-N-amidotransferase, L-asparaginase and several enzymes involved in pyrimidine and purine de novo synthesis. As a result, DON is actively used in preclinical models of cancer and neurodegenerative disease. Moreover, there have been several clinical trials using DON to treat a variety of cancers. Considerations of dose and exposure are especially important with DON treatment due to its narrow therapeutic window and significant side effects. Consequently, a robust quantification bioassay is of interest. DON is a polar unstable molecule which has made quantification challenging. Here we report on the characterization of a bioanalytical method to quantify DON in tissue samples involving DON derivatization with 3N HCl in butanol. The derivatized product is lipophilic and stable. Detection of this analyte by mass spectrometry is fast, specific and can be used to quantify DON in plasma and brain tissue with a limit of detection in the low nanomolar level. PMID:25584882

Synthesis of oxidized guar gum by dry method and its application in reactive dye printing.

PubMed

Gong, Honghong; Liu, Mingzhu; Zhang, Bing; Cui, Dapeng; Gao, Chunmei; Ni, Boli; Chen, Jiucun

2011-12-01

The aim of this study was to prepare oxidized guar gum with a simple dry method, basing on guar gum, hydrogen peroxide and a small amount of solvent. To obtain a product with suitable viscosity for reactive dye printing, the effects of various factors such as the amount of oxidant and solvent, reaction temperature and time were studied with respect to the viscosity of reaction products. The product was characterized by Fourier transform infrared spectroscopy, size exclusion chromatography, scanning electron microscopy and differential scanning calorimetry. The hydrated rate of guar gum and oxidized guar gum was estimated through measuring the required time when their solutions (1%, w/v) reached the maximum viscosity. The effects of the salt concentration and pH on viscosity of the resultant product were studied. The mixed paste containing oxidized guar gum and carboxymethyl starch was prepared and its viscosity was determined by the viscometer. The rheological property of the mixed paste was appraised by the printing viscosity index. In addition, the applied effect of mixed paste in reactive dye printing was examined by assessing the fabric stiffness, color yield and sharp edge to the printed image in comparison with sodium alginate. And the results indicated that the mixed paste could partially replace sodium alginate as thickener in reactive dye printing. The study also showed that the method was low cost and eco-friendly and the product would have an extensive application in reactive dye printing. Copyright © 2011 Elsevier B.V. All rights reserved.

Fabrication and electrical characterization of Al/diazo compound containing polyoxy chain/p-Si device structure

NASA Astrophysics Data System (ADS)

Birel, Ozgul; Kavasoglu, Nese; Kavasoglu, A. Sertap; Dincalp, Haluk; Metin, Bengul

2013-03-01

Diazo-compounds are important class of chemical compounds in terms of optical and electronic properties which make them potentially attractive for device applications. Diazo compound containing polyoxy chain has been deposited on p-Si. Current-voltage characteristics of Al/diazo compound containing polyoxy chain/p-Si structure present rectifying behaviour. The Schottky barrier height (SBH), diode factor (n), reverse saturation current (Io), interface state density (Nss) of Al/diazo compound containing polyoxy chain/p-Si structure have been calculated from experimental forward bias current-voltage data measured in the temperature range 100-320 K and capacitance-voltage data measured at room temperature and 1 MHz. The calculated values of SBH have ranged from 0.041 and 0.151 eV for the high and low temperature regions. Diode factor values fluctuate between the values 14 and 18 with temperature. Such a high diode factors stem from disordered interface layer in a junction structure as stated by Brötzmann et al. [M. Brötzmann, U. Vetter, H. Hofsäss, J. Appl. Phys. 106 (2009) 063704]. The calculated values of saturation current have ranged from 3×10-11 A to 2.79×10-7 A and interface state density have ranged from 5×1011 eV-1 cm-2 and 4×1013 eV-1 cm-2 as temperature increases. Results show that Al/diazo compound containing polyoxy chain/p-Si structure is a valuable candidate for device applications in terms of low reverse saturation current and low interface state density.

Factors influencing naproxen metabolite interference in total bilirubin assays.

PubMed

Saifee, Nabiha Huq; Ranjitkar, Pratistha; Greene, Dina N

2016-04-01

The factors influencing naproxen metabolite O-desmethylnaproxen (ODMN) positive interference in diazo-based Jendrassik and Grof (JG) total bilirubin (Tbil) assays and lack of interference in direct bilirubin (Dbil) assays have not been resolved. The objective of this study was to understand the conditions causing this interference pattern. Pooled normal and ultra-filtered plasma samples spiked with ODMN and naproxen were measured on the Beckman Coulter DxC and AU instruments. Absorbance spectra were obtained for ODMN mixed with Dbil reagent at original and adjusted pH. Absorbance spectra were also obtained for ODMN and bilirubin samples mixed with Tbil assay reagents. ODMN produces a positive interference in the DxC JG Tbil assays, but not the AU Tbil or Dbil assays or the DxC Dbil assay. Neutralizing the acidic pH of AU and DxC Dbil reagents allows ODMN to react with diazo salts. ODMN samples mixed with DxC and AU Tbil reagents produce broad peaks from 450 to 560nm and 400 to 540nm, respectively. The DxC JG Tbil assay monitors a change in absorbance at 520nm close to peak absorbance wavelength of diazo-reacted ODMN, whereas the AU Tbil assay monitors a change in absorbance at 570/660nm, beyond the peak absorbance wavelengths of diazo-reacted ODMN. The acidic pH of diazo-based Dbil assay reagents inhibits the reaction of ODMN with diazo salts. The AU JG Tbil assay is a reliable method to measure Tbil in the setting of naproxen overdose. Copyright © 2015 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

Diazo techniques for remote sensor data analysis

NASA Technical Reports Server (NTRS)

Mount, S.; Whitebay, L. E.

1979-01-01

Cost and time to extract land use maps, natural-resource surveys, and other data from aerial and satellite photographs are reduced by diazo processing. Process can be controlled to enhance features such as vegetation, land boundaries, and bodies of water.

The covalently bound diazo group as an infrared probe for hydrogen bonding environments.

PubMed

You, Min; Liu, Liyuan; Zhang, Wenkai

2017-07-26

Covalently bound diazo groups are frequently found in biomolecular substrates. The C[double bond, length as m-dash]N[double bond, length as m-dash]N asymmetric stretching vibration (ν as ) of the diazo group has a large extinction coefficient and appears in an uncongested spectral region. To evaluate the solvatochromism of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band for studying biomolecules, we recorded the infrared (IR) spectra of a diazo model compound, 2-diazo-3-oxo-butyric acid ethyl ester, in different solvents. The width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band was linearly dependent on the Kamlet-Taft solvent parameter, which reflects the polarizability and hydrogen bond accepting ability of the solvent. Therefore, the width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band could be used to probe these properties for a solvent. We found that the position of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band was linearly correlated with the density of hydrogen bond donor groups in the solvent. We studied the relaxation dynamics and spectral diffusion of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band of a natural amino acid, 6-diazo-5-oxo-l-norleucine, in water using nonlinear IR spectroscopy. The relaxation and spectral diffusion time constants of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band were similar to those of the N[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band. We concluded that the position and width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band of the diazo group could be used to probe the hydrogen bond donating and accepting ability of a solvent, respectively. These results suggest that the diazo group could be used as a site-specific IR probe for the local hydration environments.

Biosorption of reactive dye from textile wastewater by non-viable biomass of Aspergillus niger and Spirogyra sp.

PubMed

Khalaf, Mahmoud A

2008-09-01

The potential of Aspergillus niger fungus and Spirogyra sp., a fresh water green algae, was investigated as a biosorbents for removal of reactive dye (Synazol) from its multi component textile wastewater. The results showed that pre-treatment of fungal and algal biomasses with autoclaving increased the removal of dye than pre-treatment with gamma-irradiation. The effects of operational parameters (pH, temperature, biomass concentration and time) on dye removal were examined. The results obtained revealed that dried autoclaved biomass of A. niger and Spirogyra sp. exhibited maximum dye removal (88% and 85%, respectively) at pH3, temperature 30 degrees C and 8 gl(-1)(w/v) biomass conc. after 18h contact time. The stability and efficiency of both organisms in the long-term repetitive operation were also investigated. The results showed that the non-viable biomasses possessed high stability and efficiency of dye removal over 3 repeated batches.

A One-Pot Synthesis of Dibenzofurans from 6-Diazo-2-cyclohexenones.

PubMed

Zhao, Hua; Yang, Ke; Zheng, Hongyan; Ding, Ruichao; Yin, Fangjie; Wang, Ning; Li, Yun; Cheng, Bin; Wang, Huifei; Zhai, Hongbin

2015-12-04

A novel and efficient protocol for the rapid construction of dibenzofuran motifs from 6-diazo-2-cyclohexenone and ortho-haloiodobenzene has been developed. The process involves one-pot Pd-catalyzed cross-coupling/aromatization and Cu-catalyzed Ullmann coupling.

A Versatile Room-Temperature Route to Di- and Trisubstituted Allenes Using Flow-Generated Diazo Compounds**

PubMed Central

Poh, Jian-Siang; Tran, Duc N; Battilocchio, Claudio; Hawkins, Joel M; Ley, Steven V

2015-01-01

A copper-catalyzed coupling reaction between flow-generated unstabilized diazo compounds and terminal alkynes provides di- and trisubstituted allenes. This extremely mild and rapid transformation is highly tolerant of several functional groups. PMID:26013774

Refractive index modulation in polymer film doped with diazo Meldrum's acid

NASA Astrophysics Data System (ADS)

Zanutta, Alessio; Villa, Filippo; Bertarelli, Chiara; Bianco, Andrea

2016-08-01

Diazo Meldrum's acid undergoes a photoreaction induced by UV light and it is used as photosensitizer in photoresists. Upon photoreaction, a change in refractive index occurs, which makes this system interesting for volume holography. We report on the sublimation effect at room temperature and the effect of photoirradiation on the refractive index in thin films of CAB (Cellulose acetate butyrate) doped with different amount of diazo Meldrum's acid. A net modulation of the refractive index of 0.01 is achieved with 40% of doping ratio together with a reduction of the film thickness.

Synthesis of Substituted 1,4-Dioxenes through O-H Insertion and Cyclization Using Keto-Diazo Compounds.

PubMed

Davis, Owen A; Croft, Rosemary A; Bull, James A

2016-11-18

1,4-Dioxenes present interesting potential as synthetic intermediates and as unusual motifs for incorporation into biologically active compounds. Here, an efficient synthesis of functionalized 1,4-dioxenes is achieved in two steps. Using keto-diazo compounds, a ruthenium catalyzed O-H insertion with β-halohydrins followed by treatment with base results in cyclization with excellent selectivity, through O-alkylation of the keto-enolate. A variety of halohydrins and anion-stabilizing groups in the diazo-component are tolerated, affording novel functionalized dioxenes. Enantioenriched β-bromohydrins provide enantioenriched 1,4-dioxenes.

Enantioselective Synthesis of α-Mercapto-β-amino Esters via Rh(II)/Chiral Phosphoric Acid-Cocatalyzed Three-Component Reaction of Diazo Compounds, Thiols, and Imines.

PubMed

Xiao, Guolan; Ma, Chaoqun; Xing, Dong; Hu, Wenhao

2016-12-02

An enantioselective method for the synthesis of α-mercapto-β-amino esters has been developed via a rhodium(II)/chiral phosphoric acid-cocatalyzed three-component reaction of diazo compounds, thiols, and imines. This transformation is proposed to proceed through enantioselective trapping of the sulfonium ylide intermediate generated in situ from the diazo compound and thiol by the phosphoric acid-activated imine. With this method, a series of α-mercapto-β-amino esters were obtained in good yields with moderate to good stereoselectivities.

Structure of 6-diazo-5-oxo-norleucine-bound human gamma-glutamyl transpeptidase 1, a novel mechanism of inactivation.

PubMed

Terzyan, Simon S; Cook, Paul F; Heroux, Annie; Hanigan, Marie H

2017-06-01

Intense efforts are underway to identify inhibitors of the enzyme gamma-glutamyl transpeptidase 1 (GGT1) which cleaves extracellular gamma-glutamyl compounds and contributes to the pathology of asthma, reperfusion injury and cancer. The glutamate analog, 6-diazo-5-oxo-norleucine (DON), inhibits GGT1. DON also inhibits many essential glutamine metabolizing enzymes rendering it too toxic for use in the clinic as a GGT1 inhibitor. We investigated the molecular mechanism of human GGT1 (hGGT1) inhibition by DON to determine possible strategies for increasing its specificity for hGGT1. DON is an irreversible inhibitor of hGGT1. The second order rate constant of inactivation was 0.052 mM -1 min -1 and the K i was 2.7 ± 0.7 mM. The crystal structure of DON-inactivated hGGT1 contained a molecule of DON without the diazo-nitrogen atoms in the active site. The overall structure of the hGGT1-DON complex resembled the structure of the apo-enzyme; however, shifts were detected in the loop forming the oxyanion hole and elements of the main chain that form the entrance to the active site. The structure of hGGT1-DON complex revealed two covalent bonds between the enzyme and inhibitor which were part of a six membered ring. The ring included the OG atom of Thr381, the reactive nucleophile of hGGT1 and the α-amine of Thr381. The structure of DON-bound hGGT1 has led to the discovery of a new mechanism of inactivation by DON that differs from its inactivation of other glutamine metabolizing enzymes, and insight into the activation of the catalytic nucleophile that initiates the hGGT1 reaction. © 2017 The Protein Society.

Automated extraction of direct, reactive, and vat dyes from cellulosic fibers for forensic analysis by capillary electrophoresis.

PubMed

Dockery, C R; Stefan, A R; Nieuwland, A A; Roberson, S N; Baguley, B M; Hendrix, J E; Morgan, S L

2009-08-01

Systematic designed experiments were employed to find the optimum conditions for extraction of direct, reactive, and vat dyes from cotton fibers prior to forensic characterization. Automated microextractions were coupled with measurements of extraction efficiencies on a microplate reader UV-visible spectrophotometer to enable rapid screening of extraction efficiency as a function of solvent composition. Solvent extraction conditions were also developed to be compatible with subsequent forensic characterization of extracted dyes by capillary electrophoresis with UV-visible diode array detection. The capillary electrophoresis electrolyte successfully used in this work consists of 5 mM ammonium acetate in 40:60 acetonitrile-water at pH 9.3, with the addition of sodium dithionite reducing agent to facilitate analysis of vat dyes. The ultimate goal of these research efforts is enhanced discrimination of trace fiber evidence by analysis of extracted dyes.

[Determination of serum acetaminophen based on the diazo reaction and its application in the evaluation of gastric emptying].

PubMed

Li, Cai-na; Sun, Su-juan; Shen, Zhu-fang

2015-05-01

This study aims to establish a method to determine the serum acetaminophen concentration based on diazo reaction, and apply it in the gastric emptying evaluation. Theoretically, acetaminophen could take hydrolysis reaction in hydrochloric acid solution to produce p-aminophenol, which could then take diazo reaction resulting in a product with special absorption peak at 312 nm. Then the serum acetaminophen concentration and recovery rate were calculated according to the standard curve drawn with absorbance at 312 nm. ICR mice were given a dose of acetaminophen (500 mg x kg(-1)) by gavage and the serum acetaminophen was dynamically measured through the diazo reaction. Besides, ICR mice were subcutaneously injected with the long-acting GLP-1 analog GW002 before the gavage of acetaminophen, and serum acetaminophen concentration was measured as above to study how GW002 could influence the gastric emptying. The data showed acetaminophen ranging from 0 to 160 μg x mL(-1) could take diazo reaction with excellent linear relationship, and the regression equation was y = 0.0181 x +0.0104, R2 = 0.9997. The serum acetaminophen was also measured with good linear relationship (y = 0.0045 x + 0.0462, R = 0.9982) and the recovery rate was 97.4%-116.7%. The serum concentration of acetaminophen reached peak at about 0.5 h after gavage, and then gradually decreased. GW002 could significantly lower the serum acetaminophen concentration and make the area under the concentration-time curve (AUC) decrease by 28.4%. In conclusion, a method for the determination of serum acetaminophen based on the diazo reaction was established with good accuracy and could be used in the evaluation of gastric emptying.

DFT Study of the Structure, Reactivity, Natural Bond Orbital and Hyperpolarizability of Thiazole Azo Dyes

PubMed Central

Osman, Osman I.

2017-01-01

The structure, reactivity, natural bond orbital (NBO), linear and nonlinear optical (NLO) properties of three thiazole azo dyes (A, B and C) were monitored by applying B3LYP, CAM-B3LYP and ωB97XD functionals with 6-311++G** and aug-cc-pvdz basis sets. The geometrical parameters, dipole moments, HOMO-LUMO (highest occupied molecular orbital, lowest unoccupied molecular orbital) energy gaps, absorption wavelengths and total hyperpolarizabilities were investigated in carbon tetrachloride (CCl4) chloroform (CHCl3), dichloromethane (CH2Cl2) and dimethlysulphoxide (DMSO). The donor methoxyphenyl group deviates from planarity with the thiazole azo moiety by ca. 38°; while the acceptor dicyanovinyl, indandione and dicyanovinylindanone groups diverge by ca. 6°. The HOMOs for the three dyes are identical. They spread over the methoxyphenyl donor moiety, the thiazole and benzene rings as π-bonding orbitals. The LUMOs are shaped up by the nature of the acceptor moieties. The LUMOs of the A, B and C dyes extend over the indandione, malononitrile and dicyanovinylindanone acceptor moieties, respectively, as π-antibonding orbitals. The HOMO-LUMO splittings showed that Dye C is much more reactive than dyes A and B. Compared to dyes A and B, Dye C yielded a longer maximum absorption wavelength because of the stabilization of its LUMOs relative to those of the other two. The three dyes show solvatochromism accompanied by significant increases in hyperpolarizability. The enhancement of the total hyperpolarizability of C compared to those of A and B is due to the cumulative action of the long π-conjugation of the indanone ring and the stronger electron-withdrawing ability of the dicyanovinyl moiety that form the dicyanovinylindanone acceptor group. These findings are facilitated by a natural bond orbital (NBO) technique. The very high total hyperpolarizabilities of the three dyes define their potent nonlinear optical (NLO) behaviour. PMID:28157151

Consideration of Preventing Local Venous Pain by Dacarbazine.

PubMed

Ohtsubo, Tatsuya; Tsuji, Takumi; Umeyama, Takayo; Sudou, Miho; Komesu, Kana; Matsumoto, Minako; Yoshida, Yuya; Banno, Rie; Tomogane, Kanji; Fujita, Atsuo; Kohno, Takeyuki; Mikami, Tadashi

2017-01-01

Local venous pain caused by dacarbazine (DTIC) injection is due to its photodegradation product 5-diazoimidazole-4-carboxamide (Diazo-IC). The production of Diazo-IC can be decreased by protecting the drug from light. Furthermore, the production of Diazo-IC reportedly increases with time; however, there are no studies reporting the association between the injection preparation time and local venous pain caused by the DTIC injection. We evaluated the efficacy of the following: (1) method used to shorten the injection preparation time and (2) method used to change the diluting solution for DTIC. We found that shortening the injection preparation time tended to decrease the local venous pain expression due to DTIC, and Veen F decreased the production of Diazo-IC compared with the normal saline and 5% glucose solution. These results indicate that shortening the injection preparation time may be effective in preventing the local venous pain caused by the DTIC injection; moreover, using Veen F for DTIC may also reduce the pain.

Study of chemical reactivity in relation to experimental parameters of efficiency in coumarin derivatives for dye sensitized solar cells using DFT.

PubMed

Soto-Rojo, Rody; Baldenebro-López, Jesús; Glossman-Mitnik, Daniel

2015-06-07

A group of dyes derived from coumarin was studied, which consisted of nine molecules using a very similar manufacturing process of dye sensitized solar cells (DSSCs). Optimized geometries, energy levels of the highest occupied molecular orbital and the lowest unoccupied molecular orbital, and ultraviolet-visible spectra were obtained using theoretical calculations, and they were also compared with experimental conversion efficiencies of the DSSC. The representation of an excited state in terms of natural transition orbitals (NTOs) was studied. Chemical reactivity parameters were calculated and correlated with the experimental data linked to the efficiency of the DSSC. A new proposal was obtained to design new molecular systems and to predict their potential use as a dye in DSSCs.

Sorption isotherms, kinetic and optimization process of amino acid proline based polymer nanocomposite for the removal of selected textile dyes from industrial wastewater.

PubMed

Raghunath, Sharista; Anand, K; Gengan, R M; Nayunigari, Mithil Kumar; Maity, Arjun

2016-12-01

In this article, adsorption and kinetic studies were carried out on three textile dyes, namely Reactive Blue 222 (RB 222), Reactive Red 195 (RR 195) and Reactive Yellow 145 (RY 145). The dyes studied in a mixture were adsorbed under various conditions onto PRO-BEN, a bentonite modified with a new cationic proline polymer (l-proline-epichlorohydrin polymer). The proline polymer was characterized by 1 H NMR, Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS) and TEM. The PRO-BEN composite was characterized by FT-IR, dynamic light scattering (DLS) (zeta potential), TEM imaging, SEM/EDX and X-ray photoelectron spectroscopy (characterize the binding energy). During adsorption studies, factors involving pH, temperature, the initial concentrations of the dyes and the quantity of PRO-BEN used during adsorption were established. The results revealed that the adsorption mechanism was categorized by the Langmuir type 1 isotherm. The adsorption data followed the pseudo-second order kinetic model. The intraparticle diffusion model indicated that adsorption did not only depend on the intraparticle diffusion of the dyes. The thermodynamic parameters verified that the adsorption process was spontaneous and exothermic. The Gibbs free energy values indicated that physisorption had occurred. Successful adsorption of dyes from an industrial effluent was achieved. Desorption studies concluded that PRO-BEN desorbed the dyes better than alumina. This can thereby be viewed as a recyclable remediation material. The PRO-BEN composite could be a cost efficient alternative towards the removal of organic dyes in wastewater treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Typhidot M and Diazo test vis-à-vis blood culture and Widal test in the early diagnosis of typhoid fever in children in a resource poor setting.

PubMed

Beig, Farzana K; Ahmad, Faraz; Ekram, Mohd; Shukla, Indu

2010-01-01

Typhoid fever is a major public health problem. A test which is simple, reliable and can be carried out in small laboratories is the need of the hour. We prospectively evaluated typhidot M and Diazo tests vis-à-vis blood culture and Widal test in children. Patients aged 6 months to 12 years, having fever of more than four days duration with clinical suspicion of typhoid fever were enrolled. Patients in whom other diagnosis was made served as control. The tests under scrutiny were validated against blood culture and then all the four tests were evaluated among patients who presented in the first week of illness. Blood culture was positive in only 27.3% of the cases. Among these culture positive cases, typhidot M test had the highest sensitivity, specificity, PPV and NPV of 90% (95% CI = 74.4-96.5), 100% (95% CI = 90.1-100), 100% (95% CI = 87.5-100), and 92.1% (95% CI = 79.2-97.3) respectively. Diazo test ranked next with sensitivity, specificity, PPV and NPV of 86.7% (95% CI = 70.3-94.7), 85.7% (95% CI = 70.6-93.7), 83.9% (95% CI = 67.4-92.9), 88.2% (95% CI = 73.4-95.3) respectively. Among clinically suspected typhoid cases, the overall sensitivity, of blood culture, Widal, typhidot M, Diazo was 27.3% (95% CI = 19.8- 36.3), 64.6% (95% CI = 55.3-72.9), 89.1% (95% CI = 81.9-93.7), 80.9% (95% CI = 72.6-87.2) respectively. In the first week of illness, typhidot M showed the best sensitivity [86.2% (95% CI = 69.4-94.5)] followed by Diazo [79% (95% CI = 61.6-90.2)], Widal [41.4% (95% CI = 25.5-59.3)] and blood culture [31% (95% CI = 17.3-49.2)]. Both Typhidot M and Diazo are good screening tests for the diagnosis of typhoid fever. Typhidot M is superior to Diazo but the latter is more suitable to resource poor settings being economic and easy to perform.

Effect of trace metals and electron shuttle on simultaneous reduction of reactive black-5 azo dye and hexavalent chromium in liquid medium by Pseudomonas sp.

PubMed

Mahmood, Shahid; Khalid, Azeem; Arshad, Muhammad; Ahmad, Riaz

2015-11-01

This study demonstrates the role of electron shuttles and trace metals in the biotransformation of azo dye reactive black-5 and hexavalent chromium (CrVI) that are released simultaneously in tannery effluent. Previously isolated bacterial strain Pseudomonas putida KI was used for the simultaneous reduction of the dye (100 mg L(-1)) and CrVI (2 mg L(-1)) in a mineral salts medium (MSM). Among various trace metals, only Cu(II) had a stimulating effect on the bacterial-mediated reduction process. Application of electron shuttles such as hydroquinone and uric acid at a low concentration (1mM) had a positive effect on the reduction process and caused simultaneous reduction of 100% dye and 97% CrVI in 12-18 h. Mannitol, EDTA and sodium benzoate at all concentrations (ranging from 1 to 9 mM) showed an inhibitory effect on the reduction of reactive black-5 and CrVI. An inverse linear relationship between the velocity of reaction (V) and the concentration [S] of electron shuttles was observed. The results imply that both types and concentration of an electron shuttle and trace metals can affect the simultaneous reduction of reactive black-5 and CrVI. Copyright © 2014 Elsevier Ltd. All rights reserved.

Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

PubMed

Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

2015-12-01

This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

Treatment of complex Remazol dye effluent using sawdust- and coal-based activated carbons.

PubMed

Vijayaraghavan, K; Won, Sung Wook; Yun, Yeoung-Sang

2009-08-15

A complex Remazol dye effluent, comprised of four reactive dyes and auxiliary chemicals, was decolorized using SPS-200 (sawdust-based) and SPC-100 (coal-based) activated carbons. A detailed characterization revealed that the pore diameter of the activated carbon played an important role in dye adsorption. The solution pH had no significant effect on the adsorption capacity in the pH range of 2-10.7. According to the Langmuir model, the maximum uptakes of SPS-200 were 415.4, 510.3, 368.5 and 453.0 mg g(-1) for Reactive Black 5 (RB5), Reactive Orange 16 (RO16), Remazol Brilliant Blue R (RBBR) and Remazol Brilliant Violet 5R (RBV), respectively. Conversely, those of SPC-100 were slightly lower, at 150.8, 197.4, 178.3 and 201.1 mg g(-1) for RB5, RO16, RBBR and RBV, respectively. In the case of Remazol effluent, SPS-200 exhibited a decolorization efficiency of 100% under unadjusted pH conditions at 10.7, compared to that of 52% for SPC-100.

Adsorption of Reactive Red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon.

PubMed

Machado, Fernando M; Bergmann, Carlos P; Fernandes, Thais H M; Lima, Eder C; Royer, Betina; Calvete, Tatiana; Fagan, Solange B

2011-09-15

Multi-walled carbon nanotubes and powdered activated carbon were used as adsorbents for the successful removal of Reactive Red M-2BE textile dye from aqueous solutions. The adsorbents were characterised by infrared spectroscopy, N(2) adsorption/desorption isotherms and scanning electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium at 298K was fixed at 1h for both adsorbents. The activation energy of the adsorption process was evaluated from 298 to 323K for both adsorbents. The Avrami fractional-order kinetic model provided the best fit to the experimental data compared with pseudo-first-order or pseudo-second-order kinetic adsorption models. For Reactive Red M-2BE dye, the equilibrium data were best fitted to the Liu isotherm model. Simulated dyehouse effluents were used to check the applicability of the proposed adsorbents for effluent treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

Techno-economical optimization of Reactive Blue 19 removal by combined electrocoagulation/coagulation process through MOPSO using RSM and ANFIS models.

PubMed

Taheri, M; Alavi Moghaddam, M R; Arami, M

2013-10-15

In this research, Response Surface Methodology (RSM) and Adaptive Neuro Fuzzy Inference System (ANFIS) models were applied for optimization of Reactive Blue 19 removal using combined electrocoagulation/coagulation process through Multi-Objective Particle Swarm Optimization (MOPSO). By applying RSM, the effects of five independent parameters including applied current, reaction time, initial dye concentration, initial pH and dosage of Poly Aluminum Chloride were studied. According to the RSM results, all the independent parameters are equally important in dye removal efficiency. In addition, ANFIS was applied for dye removal efficiency and operating costs modeling. High R(2) values (≥85%) indicate that the predictions of RSM and ANFIS models are acceptable for both responses. ANFIS was also used in MOPSO for finding the best techno-economical Reactive Blue 19 elimination conditions according to RSM design. Through MOPSO and the selected ANFIS model, Minimum and maximum values of 58.27% and 99.67% dye removal efficiencies were obtained, respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

Investigation of applicability of Electro-Fenton method for the mineralization of naphthol blue black in water.

PubMed

Özcan, Ayça Atılır; Özcan, Ali

2018-07-01

In this study, mineralization and color removal performance of electro-Fenton method were examined in water containing naphthol blue black (NBB), a diazo dye. NBB was totally converted to intermediate species in a 15-min electrolysis at 60 mA, but complete de-colorization took 180 min. A very high oxidation rate constant ((3.35 ± 0.21) x 10 10  M -1 s -1 ) was obtained for NBB, showing its high reactivity towards hydroxyl radicals. A very high total organic carbon (TOC) removal value (45.23 mg L -1 ) was obtained in the first 60 min of the electro-Fenton treatment of an aqueous solution of NBB (0.25 mM) at 300 mA, indicating the mineralization efficiency of the electro-Fenton method. Mineralization current efficiency values obtained at 300 mA gradually decreased from 24.18% to 4.47% with the electrolysis time, indicating the presence of highly parasitic reactions. Gas chromatography-mass spectrometry analyses revealed that the cleavage of azo bonds of NBB led to formation of different aromatic and aliphatic oxidation intermediates. Ion chromatography analysis showed that ammonium, nitrate and sulfate were the mineralization end-products. The concentration of sulfate ion reached to its quantitative value at the 4th h of electrolysis. On the other hand, the total concentration of ammonium and nitrate ions reached to only 61% of the stoichiometric amount of initial nitrogen after a 7 h electrolysis. Finally, it can be said that the electro-Fenton method is a suitable and efficient method for the removal of NBB and its intermediates from water. Copyright © 2018 Elsevier Ltd. All rights reserved.

Treatment of textile dyehouse effluent using ceramic membrane based process in combination with chemical pretreatment.

PubMed

Bhattacharya, Priyankari; Ghosh, Sourja; Majumdar, Swachchha; Bandyopadhyay, Sibdas

2013-10-01

Treatment of highly concentrated dyebath effluent and comparatively dilute composite effluent having mixture of various reactive dyes collected from a cotton fabric dyeing unit was undertaken in the present study. Ceramic microfiltration membrane prepared from a cost effective composition of alumina and clay was used. Prior to microfiltration, a chemical pretreatment was carried out with aluminium sulphate in combination with a polymeric retention aid. An optimum dose of 100 mg/L of aluminium sulphate and 1 ml/L of a commercial flocculant Afilan RAMF was found effective for dye removal (> 98%) from the synthetic solutions of reactive dyes with initial concentration of 150 mg/L in both the single component and two component systems. In the microfiltration study, effect of operating pressure in the permeate flux was observed for both the pretreated and untreated effluents and permeate samples were analyzed for dye concentration, COD, turbidity, TSS, etc. during constant pressure filtration. About 98-99% removal of dyes was obtained in the combined process with COD reduction of 54-64%.

18. Photocopy of drawing (22 x 34 inch diazo located ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

18. Photocopy of drawing (22 x 34 inch diazo located in the recreation files, Mt. Baker-Snoqualmie N. F.). G. STAVI, 1970. 1ST & 2ND FLOOR PLANS, ALTERATIONS TO CASCADE FILED STATION, GLACIER, WASHINGTON. - Austin Pass Warming Hut, Washington Highway 542, Glacier, Whatcom County, WA

Archival Stability of Microfilm.

ERIC Educational Resources Information Center

Materazzi, Albert R.

This report is in response to complaints and criticism by the library community on the Superintendent of Documents' decision to furnish third generation diazo microfiche for the Depository Library program. It reviews some of the basic photographic chemistry of both silver halides and diazos which have an influence on dark stability. A review of…

Practical Microform Materials for Libraries: Silver, Diazo, Vesicular.

ERIC Educational Resources Information Center

Veaner, Allen B.

1982-01-01

Remarks on the relative permanence and durability of three types of film in use in library microform reproduction (silver, diazo, and vesicular) and points out some technical and economic facts that govern the choice of microform materials for libraries. A 6-item reference list is included. (Author/JL)

Toxicological Assessment and UV/TiO2-Based Induced Degradation Profile of Reactive Black 5 Dye

NASA Astrophysics Data System (ADS)

Bilal, Muhammad; Rasheed, Tahir; Iqbal, Hafiz M. N.; Hu, Hongbo; Wang, Wei; Zhang, Xuehong

2018-01-01

In this study, the toxicological and degradation profile of Reactive Black 5 (RB5) dye was evaluated using a UV/TiO2-based degradation system. Fourier transform infrared spectroscopy (FT-IR), thin layer chromatography (TLC), high-performance liquid chromatography (HPLC) and ultra-performance liquid chromatography coupled with mass spectrometry (UPLC-MS) techniques were used to evaluate the degradation level of RB5. The UV-Vis spectral analysis revealed the disappearance of peak intensity at 599 nm (λmax). The FT-IR spectrum of UV/TiO2 treated dye sample manifest appearance of new peaks mainly because of the degraded product and/or disappearance of some characteristics peaks which were present in the untreated spectrum. The HPLC profile verified the RB5 degradation subject to the formation of metabolites at different retention times. A stable color removal higher than 96% with COD removal in the range of 74-82.3% was noted at all evaluated dye concentrations. The tentative degradation pathway of RB5 is proposed following a careful analysis of the intermediates identified by UPLC-MS. Toxicity profile of untreated and degraded dye samples was monitored using three types of human cell lines via MTT assay and acute toxicity testing with Artemia salina. In conclusion, the UV/TiO2-based degradation system could be effectively employed for the remediation of textile wastewater comprising a high concentration of reactive dyes.

Ruthenium(II)-Catalyzed C-H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate-Controlled Synthesis of Indoles and 3H-Indoles.

PubMed

Li, Yunyun; Qi, Zisong; Wang, He; Yang, Xifa; Li, Xingwei

2016-09-19

Indoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor-acceptor diazo compounds were developed that afforded NH indoles and 3H-indoles under ruthenium catalysis. The coupling of α-diazoketoesters afforded NH indoles by cleavage of the C(N2 )-C(acyl) bond whereas α-diazomalonates gave 3H-indoles by C-N bond cleavage. This reaction constitutes the first intermolecular coupling of diazo substrates with arenes by ruthenium-catalyzed C-H activation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process Improvement of Reactive Dye Synthesis Using Six Sigma Concept

NASA Astrophysics Data System (ADS)

Suwanich, Thanapat; Chutima, Parames

2017-06-01

This research focuses on the problem occurred in the reactive dye synthesis process of a global manufacturer in Thailand which producing various chemicals for reactive dye products to supply global industries such as chemicals, textiles and garments. The product named “Reactive Blue Base” is selected in this study because it has highest demand and the current chemical yield shows a high variation, i.e. yield variation of 90.4% - 99.1% (S.D. = 2.405 and Cpk = -0.08) and average yield is 94.5% (lower than the 95% standard set by the company). The Six Sigma concept is applied aiming at increasing yield and reducing variation of this process. This approach is suitable since it provides a systematic guideline with five improvement phases (DMAIC) to effectively tackle the problem and find the appropriate parameter settings of the process. Under the new parameter settings, the process yield variation is reduced to range between 96.5% - 98.5% (S.D. = 0.525 and Cpk = 1.83) and the average yield is increased to 97.5% (higher than the 95% standard set by the company).

Azidoimidazolinium Salts: Safe and Efficient Diazo-transfer Reagents and Unique Azido-donors.

PubMed

Kitamura, Mitsuru

2017-07-01

2-Azido-1,3-dimethylimidazolinium chloride (ADMC) and its corresponding hexafluorophosphate (ADMP) were found to be efficient diazo-transfer reagents to various organic compounds. ADMC was prepared by the reaction of 2-chloro-1,3-dimethylimidazolinium chloride (DMC) and sodium azide. ADMP was isolated as a crystal having good thermal stability and low explosibility. ADMC and ADMP reacted with 1,3-dicarbonyl compounds under mild basic conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which were easily isolated in virtue of the high water solubility of the by-products. ADMP showed high diazo-transfer ability to primary amines even in the absence of metal salt such as Cu(II). Using this diazotization approach, various alkyl/aryl azides were directly obtained from their corresponding primary amines in high yields. Furthermore, naphthols reacted with ADMC to give the corresponding diazonaphthoquinones in good to high yields. In addition, 2-azido-1,3-dimethylimidazolinium salts were employed as azide-transfer and migratory amidation reagents. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of carboxymethyl potato starch and its application in reactive dye printing.

PubMed

Zhang, Bing; Gong, Honghong; Lü, Shaoyu; Ni, Boli; Liu, Mingzhu; Gao, Chunmei; Huang, Yinjuan; Han, Fei

2012-11-01

Carboxymethyl potato starch (CMPS) was synthesized with a simple dry and multi-step method as a product of the reaction of native potato starch and monochloroacetic acid in the presence of sodium hydroxide. The influence of the molar ratio of sodium hydroxide to anhydroglucose unit, the volume of 95% (v/v) ethanol, the rotation rate of motor driven stirrer and the reaction time for degree of substitution (DS) were evaluated. The product was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray diffractometry (XRD). FTIR spectrometry showed new bonds at 1618 and 1424 cm⁻¹ when native starch underwent carboxymethylation. SEM pictures showed that the smooth surface of native starch particles was mostly ruptured. XRD revealed that starch crystallinity was reduced after carboxymethylation. The viscosity of the mixture paste of carboxymethyl starch and sodium alginate (SA) was measured using a rotational viscometer. In addition, the applied effect of mixed paste in reactive dye printing was examined by assessing the fabric stiffness, color yield and sharp edge to the printed image in comparison with SA. And the results indicated that the mixed paste could partially replace SA as thickener in reactive dye printing. The study also showed that the method was low cost and eco-friendly and the product would have an extensive application in reactive dye printing. Copyright © 2012 Elsevier B.V. All rights reserved.

Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

PubMed

Xiao, Qing; Zhang, Yan; Wang, Jianbo

2013-02-19

Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo compounds or N-tosylhydrazones show that these transformations also work with other transition metals, demonstrating the generality of the diazo compounds as new cross-coupling partners in transition-metal-catalyzed coupling reactions.

Facile synthesis of fluorescent polymer nanoparticles by covalent modification-nanoprecipitation of amine-reactive ester polymers.

PubMed

Lee, Yeonju; Hanif, Sadaf; Theato, Patrick; Zentel, Rudolf; Lim, Jeewoo; Char, Kookheon

2015-06-01

Emission wavelength control in fluorescent nanoparticles (NPs) is crucial for their applications. In the case of inorganic quantum dots or dye-impregnated silica NPs, such a control is readily achieved by changing the size of the particles or choosing appropriate fluorescent dyes, respectively. A similar modular approach for controlling the emission wavelength of fluo-rescent polymer NPs, however, is difficult. This article reports on fluorescent polymer NPs, the synthesis of which provides a platform for a modular approach towards the preparation of fluorescent NPs of desired emission wavelength. Atom-transfer radical polymerization (ATRP) is employed to synthesize reactive ester polymers, which are then easily modified with a commercially available dye and subsequently subjected to nanoprecipitation. The resulting NPs, with low size polydispersity, show an enhanced emission quantum yield when compared with the same dye molecules in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequential batch culture studies for the decolorisation of reactive dye by Coriolus versicolor.

PubMed

Sanghi, Rashmi; Dixit, Awantika; Guha, Sauymen

2006-02-01

The white rot fungus Coriolus versicolor could decolorise reactive dye Remazol Brilliant Violet to almost 90%. The fungal mycelia removed color as well as COD up to 95% and 75%, respectively, in a batch reactor. Decolorising activity was observed during the repeated reuse of the fungus. It was possible to substantially increase the dye decolorising activity of the fungus by carefully selecting the operational conditions such as media composition, age of fungus and nitrogen source. The fungal pellets could be used for eight cycles during the long term operation, where medium and dye was replenished at the end of each cycle and the fungus was recycled. Presence of a nitrogen source and nutrient content of media played an important role in sustaining the decolorisation activity of the fungus. The form of nitrogen source (e.g. peptone vs. urea) was also important to maintain the decolorising activity with peptone showing better decolorisation.

An optimized assay of specific IgE antibodies to reactive dyes and studies of immunologic responses in exposed workers.

PubMed

Wass, U; Nilsson, R; Nordlinder, R; Belin, L

1990-03-01

Methods of assaying reactive dye-specific IgE antibodies were investigated with a RAST. Sera from three patients, occupationally exposed to a reactive dye, Remazol black B (Chemical Abstract registry number 17095-24-8), were used. Directly dyed disks, that is, disks without any carrier protein, resulted in poor and unreliable measures of specific IgE. In contrast, optimized preparation of conjugates between the dye and human serum albumin resulted in efficient binding of specific IgE. The patients' RAST results were strongly positive, whereas sera from 36 exposed workers but without symptoms and sera from unexposed subjects with high levels of total IgE were negative. The hapten and carrier specificity of the IgE antibodies was studied by direct RAST and RAST inhibition. In one patient, the antibodies were principally hapten specific, whereas another patient was found to have antibodies with a high degree of specificity to the carrier. The third patient's antibodies were intermediate between the other two patients' antibodies in this respect, suggesting that antibody specificity is dependent not only on the nature of the hapten but also on individual immune response factors. The study demonstrates that it is important to use an optimized preparation of dye-protein conjugates to elicit reliable results and a high degree of specific IgE binding in the RAST.

Adsorption of reactive blue BF-5G dye by soybean hulls: kinetics, equilibrium and influencing factors.

PubMed

Honorio, Jacqueline Ferandin; Veit, Márcia Teresinha; Gonçalves, Gilberto da Cunha; de Campos, Élvio Antonio; Fagundes-Klen, Márcia Regina

2016-01-01

The textile industry is known for the high use of chemicals, such as dyes, and large volumes of effluent that contaminate waters, a fact that has encouraged research and improved treatment techniques. In this study, we used unprocessed soybean hulls for the removal of reactive blue BF-5G dye. The point of zero charge of soybean hulls was 6.76. Regarding the speed of agitation in the adsorption process, the resistance to mass transfer that occurs in the boundary layer was eliminated at 100 rpm. Kinetics showed an experimental amount of dye adsorbed at equilibrium of 57.473 mg g(-1) obtained under the following conditions: dye initial concentration = 400 mg L(-1); diameter of particle = 0.725 mm; dosage = 6 g L(-1); pH 2; 100 rpm; temperature = 30 °C; and duration of 24 hours. The pseudo-second order best showed the dye removal kinetics. The adsorption isotherms performed at different temperatures (20, 30, 40 and 50 °C) showed little variation in the concentration range assessed, being properly adjusted by the Langmuir isotherm model. The maximum capacity of dye adsorption was 72.427 mg g(-1) at 30 °C. Since soybean hull is a low-cost industrial byproduct, it proved to be a potential adsorbent for the removal of the textile dye assessed.

Textile dyes induce toxicity on zebrafish early life stages.

PubMed

de Oliveira, Gisele Augusto Rodrigues; de Lapuente, Joaquín; Teixidó, Elisabet; Porredón, Constança; Borràs, Miquel; de Oliveira, Danielle Palma

2016-02-01

Textile manufacturing is one of the most polluting industrial sectors because of the release of potentially toxic compounds, such as synthetic dyes, into the environment. Depending on the class of the dyes, their loss in wastewaters can range from 2% to 50% of the original dye concentration. Consequently, uncontrolled use of such dyes can negatively affect human health and the ecological balance. The present study assessed the toxicity of the textile dyes Direct Black 38 (DB38), Reactive Blue 15 (RB15), Reactive Orange 16 (RO16), and Vat Green 3 (VG3) using zebrafish (Danio rerio) embryos for 144 h postfertilization (hpf). At the tested conditions, none of the dyes caused significant mortality. The highest RO16 dose significantly delayed or inhibited the ability of zebrafish embryos to hatch from the chorion after 96 hpf. From 120 hpf to 144 hpf, all the dyes impaired the gas bladder inflation of zebrafish larvae, DB38 also induced curved tail, and VG3 led to yolk sac edema in zebrafish larvae. Based on these data, DB38, RB15, RO16, and VG3 can induce malformations during embryonic and larval development of zebrafish. Therefore, it is essential to remove these compounds from wastewater or reduce their concentrations to safe levels before discharging textile industry effluents into the aquatic environment. © 2015 SETAC.

Biosorption of textile dye reactive blue 221 by capia pepper (Capsicum annuum L.) seeds.

PubMed

Gürel, Levent

2017-04-01

Peppers are very important foodstuffs in the world for direct and indirect consumption, so they are extensively used. The seeds of these peppers are waste materials that are disposed of from houses and factories. To evaluate the performance of this biomass in the treatment of wastewaters, a study was conducted to remove a textile dye, reactive blue 221, which is commercially used in textile mills. Raw seed materials were used without any pre-treatment. The effects of contact time, initial concentration of dye, pH and dose of biosorbent were studied to determine the optimum conditions for this biomass on color removal from wastewaters. The optimum pH value for dye biosorption was found to be 2.0. At an initial dye concentration of 217 mg L -1 , treatment efficiency and biosorption capacity were 96.7% and 95.35 mg g -1 , respectively. A maximum biosorption capacity of 142.86 mg g -1 was also obtained. Equilibrium biosorption of dye by capia seeds was well described by the Langmuir isotherm with a correlation coefficient above 99%. The biosorption process was also successfully explained with the pseudo-second order kinetic model. This biomass was found to be effective in terms of textile dye removal from aqueous solutions.

A Technical, User and Cost Comparison Study of Microfiche Duplicate Film Material. Final Report.

ERIC Educational Resources Information Center

Prevel, James J.

A technical, user and cost comparison study was undertaken to provide the Educational Resources Information Clearinghouse (ERIC) staff with data on silver halide, diazo, and vesicular type films for microfiche duplication. This information will allow ERIC to determine if diazo and/or vesicular films should be considered in producing ERIC duplicate…

Silver-Catalyzed [2+1] Cyclopropenation of Alkynes with Unstable Diazoalkanes: N-Nosylhydrazones as Room-Temperature Decomposable Diazo Surrogates.

PubMed

Liu, Zhaohong; Li, Qiangqiang; Liao, Peiqiu; Bi, Xihe

2017-04-06

The [2+1] cycloaddition of alkynes with diazo compounds represents one of the most powerful and reliable methods for the construction of cyclopropenes. However, it remains a formidable challenge to accomplish the cyclopropenation of alkynes with non-stabilized diazoalkanes, owing to the fact that such compounds are unstable and prone to detonation. Herein, we report a general silver-catalyzed cyclopropenation reaction of alkynes with unstable diazoalkanes, by for the first time the discovery and application of N-nosylhydrazones as room-temperature decomposiable diazo surrogates. This method allows for the efficient assembly a wide variety of cyclopropene derivatives that are otherwise difficult to access by conventional methods. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical Study on Vibrational Spectra, Detonation Properties and Pyrolysis Mechanism for Cyclic 2-Diazo-4,6-dinitrophenol

NASA Astrophysics Data System (ADS)

Li, Xiao-hong; Yin, Geng-xin; Zhang, Xian-zhou

2012-10-01

Based on the full optimized molecular geometrical structures at the DFT-B3LYP/6-311+G** level, there exists intramolecular hydrogen bond interaction for cyclic 2-diazo-4,6-dinitrophenol. The assigned infrared spectrum is obtained and used to compute the thermodynamic properties. The results show that there are four main characteristic regions in the calculated IR spectra of the title compound. The detonation velocities and pressures are also evaluated by using Kamlet-Jacobs equations based on the calculated density and condensed phase heat of formation. Thermal stability and the pyrolysis mechanism of 2-diazo-4,6-dinitrophenol are investigated by calculating the bond dissociation energies at the B3LYP/6-311+G** level.

Asymmetric Radical Cyclopropanation of Alkenes with In Situ-Generated Donor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis.

PubMed

Wang, Yong; Wen, Xin; Cui, Xin; Wojtas, Lukasz; Zhang, X Peter

2017-01-25

Donor-substituted diazo reagents, generated in situ from sulfonyl hydrazones in the presence of base, can serve as suitable radical precursors for Co(II)-based metalloradical catalysis (MRC). The cobalt(II) complex of D 2 -symmetric chiral porphyrin [Co(3,5-Di t Bu-Xu(2'-Naph)Phyrin)] is an efficient metalloradical catalyst that is capable of activating different N-arylsulfonyl hydrazones for asymmetric radical cyclopropanation of a broad range of alkenes, affording the corresponding cyclopropanes in high yields with effective control of both diastereo- and enantioselectivity. This Co(II)-based metalloradical system represents the first catalytic protocol that can effectively utilize donor-type diazo reagents for asymmetric olefin cyclopropanation.

Zinc oxide-mediated photocatalytic decolorization of Ponceau S in aqueous suspension by visible light

NASA Astrophysics Data System (ADS)

Muslim, Muhammad; Habib, Md Ahsan; Mahmood, Abu Jafar; Islam, Tajmeri Selima Akhter; Ismail, Iqbal Mohmmad Ibrahim

2012-10-01

ZnO, comprising nanosize particles (approximately 40 nm) has been prepared by heating (300°C) ZnCO3, which was obtained as precipitate by mixing ZnSO4 and (NH4)2CO3 solutions. The prepared ZnO was characterized by X-ray diffraction, scanning electron microscopy (SEM), laser-induced breakdown spectroscopy, and adsorption studies. It has been used to catalyze the decolorization of Ponceau S (PS), a model diazo dye, in an aqueous suspension under visible light ( I ≈ 1.8 × 10-4 W cm-2). This ZnO was found to be more efficient as a photocatalyst compared to pristine ZnO. ZnO samples with higher temperatures (500°C and 700°C) show less catalytic activity. SEM images show that the particle size of ZnO increases with the increase in calcined temperature of ZnO through agglomeration, resulting in a decrease in surface area. Photodecolorization of PS is affected by its and ZnO concentrations, but unaffected by the initial pH of the solutions in the range of 4 to 7. Illumination for a sufficiently long time completely mineralizes the dye, but no Zn2+ can be detected in the clear solution. Photodegradation kinetics in the ZnO suspension obeys the Langmuir-Hinshelwood equation, and some activation of the ZnO surface by light is indicated.

Synthesis, Characterization and Reactivity of Nanostructured Zero-Valent Iron Particles for Degradation of Azo Dyes

NASA Astrophysics Data System (ADS)

Mikhailov, Ivan; Levina, Vera; Leybo, Denis; Masov, Vsevolod; Tagirov, Marat; Kuznetsov, Denis

Nanostructured zero-valent iron (NSZVI) particles were synthesized by the method of ferric ion reduction with sodium borohydride with subsequent drying and passivation at room temperature in technical grade nitrogen. The obtained sample was characterized by means of X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and dynamic light scattering studies. The prepared NSZVI particles represent 100-200nm aggregates, which consist of 20-30nm iron nanoparticles in zero-valent oxidation state covered by thin oxide shell. The reactivity of the NSZVI sample, as the removal efficiency of refractory azo dyes, was investigated in this study. Two azo dye compounds, namely, orange G and methyl orange, are commonly detected in waste water of textile production. Experimental variables such as NSZVI dosage, initial dye concentration and solution pH were investigated. The kinetic rates of degradation of both dyes by NSZVI increased with the decrease of solution pH from 10 to 3 and with the increase of NSZVI dosage, but decreased with the increase of initial dye concentration. The removal efficiencies achieved for both orange G and methyl orange were higher than 90% after 80min of treatment.

Iterative reactions of transient boronic acids enable sequential C-C bond formation

NASA Astrophysics Data System (ADS)

Battilocchio, Claudio; Feist, Florian; Hafner, Andreas; Simon, Meike; Tran, Duc N.; Allwood, Daniel M.; Blakemore, David C.; Ley, Steven V.

2016-04-01

The ability to form multiple carbon-carbon bonds in a controlled sequence and thus rapidly build molecular complexity in an iterative fashion is an important goal in modern chemical synthesis. In recent times, transition-metal-catalysed coupling reactions have dominated in the development of C-C bond forming processes. A desire to reduce the reliance on precious metals and a need to obtain products with very low levels of metal impurities has brought a renewed focus on metal-free coupling processes. Here, we report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting flow-generated diazo compounds with boronic acids, and their application in controlled iterative C-C bond forming reactions is described. Thus far we have shown the formation of up to three C-C bonds in a sequence including the final trapping of a reactive boronic acid species with an aldehyde to generate a range of new chemical structures.

Short Time Exposure (STE) test in conjunction with Bovine Corneal Opacity and Permeability (BCOP) assay including histopathology to evaluate correspondence with the Globally Harmonized System (GHS) eye irritation classification of textile dyes.

PubMed

Oliveira, Gisele Augusto Rodrigues; Ducas, Rafael do Nascimento; Teixeira, Gabriel Campos; Batista, Aline Carvalho; Oliveira, Danielle Palma; Valadares, Marize Campos

2015-09-01

Eye irritation evaluation is mandatory for predicting health risks in consumers exposed to textile dyes. The two dyes, Reactive Orange 16 (RO16) and Reactive Green 19 (RG19) are classified as Category 2A (irritating to eyes) based on the UN Globally Harmonized System for classification (UN GHS), according to the Draize test. On the other hand, animal welfare considerations and the enforcement of a new regulation in the EU are drawing much attention in reducing or replacing animal experiments with alternative methods. This study evaluated the eye irritation of the two dyes RO16 and RG19 by combining the Short Time Exposure (STE) and the Bovine Corneal Opacity and Permeability (BCOP) assays and then comparing them with in vivo data from the GHS classification. The STE test (first level screening) categorized both dyes as GHS Category 1 (severe irritant). In the BCOP, dye RG19 was also classified as GHS Category 1 while dye RO16 was classified as GHS no prediction can be made. Both dyes caused damage to the corneal tissue as confirmed by histopathological analysis. Our findings demonstrated that the STE test did not contribute to arriving at a better conclusion about the eye irritation potential of the dyes when used in conjunction with the BCOP test. Adding the histopathology to the BCOP test could be an appropriate tool for a more meaningful prediction of the eye irritation potential of dyes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nondestructive identification of dye mixtures in polyester and cotton fibers using raman spectroscopy and ultraviolet-visible (UV-Vis) microspectrophotometry.

PubMed

Was-Gubala, Jolanta; Starczak, Roza

2015-01-01

Presented in this paper is an assessment of the applicability of Raman spectroscopy and microspectrophotometry (MSP) in visible and ultraviolet light (UV-Vis) in the examination of textile fibers dyed with mixtures of synthetic dyes. Fragments of single polyester fibers, stained with ternary mixtures of disperse dyes in small mass concentrations, and fragments of single cotton fibers, dyed with binary or ternary mixtures of reactive dyes, were subjected to the study. Three types of excitation sources, 514, 633, and 785 nm, were used during Raman examinations, while the MSP study was conducted in the 200 to 800 nm range. The results indicate that the capabilities for discernment of dye mixtures are similar in the spectroscopic methods that were employed. Both methods have a limited capacity to distinguish slightly dyed polyester fiber; additionally, it was found that Raman spectroscopy enables identification of primarily the major components in dye mixtures. The best results, in terms of the quality of Raman spectra, were obtained using an excitation source from the near infrared. MSP studies led to the conclusion that polyester testing should be carried out in the range above 310 nm, while for cotton fibers there is no limitation or restriction of the applied range. Also, MSP UV-Vis showed limited possibilities for discriminatory analysis of cotton fibers dyed with a mixture of reactive dyes, where the ratio of the concentration of the main dye used in the dyeing process to minor dye was higher than four. The results presented have practical applications in forensic studies, inter alia.

Evidence for Interfacial Halogen Bonding.

PubMed

Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

2016-05-10

A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Methods for reducing dacarbazine photodegradation and its accompanying venous pain].

PubMed

Tsuji, Takumi; Ohtsubo, Tatsuya; Umeyama, Takayo; Sudou, Miho; Komesu, Kana; Matsumoto, Minako; Yoshida, Yuya; Banno, Rie; Mikami, Tadashi; Kohno, Takeyuki

2014-01-01

The anticancer drug dacarbazine (DTIC) is photosensitive, and the photodegradation product 5-diazoimidazole-4-carboxamide (diazo-IC) induces adverse reactions including local venous pain during intravenous injection. In this study we evaluated the effectiveness of colored shields (orange and red) to protect against photodegradation of DTIC as determined by ascertaining the concentration of diazo-IC. Samples were prepared and stored under four conditions: (1) no shield; (2) covered with an aluminum (opaque) shield; (3) covered with an orange shield; and (4) covered with a red shield. The samples were exposed to natural light for a specified time (0, 30, 60, 120, and 180 min) prior to measuring the concentration of diazo-IC by HPLC. We found that after 180 min, the diazo-IC concentration was 5.7±0.6 (S.D.) μg/mL with no shield and 1.9±0.2 μg/mL in both colored shield conditions. This production of diazo-IC under the colored shields was suppressed to a level similar to that under the aluminum shield (1.7±0.2 μg/mL). We also evaluated the effectiveness of NSAIDs (zaltoprofen, loxoprofen sodium, and diclofenac sodium) administered to mice prior to DTIC treatment on venous pain by counting their stretching and writhing reactions. Premedication with zaltoprofen significantly decreased expression of pain behavior in the DTIC-treated mice. These results suggest that storing DTIC under the protection of an orange or red shield is clinically beneficial because the shield prevents DTIC photodegradation, and that NSAIDs such as zaltoprofen are a promising premedication candidate for pain.

The roles of ozone and zeolite on reactive dye degradation in electrical discharge reactors.

PubMed

Peternel, L; Kusic, H; Koprivanac, N; Locke, B R

2006-05-01

In this study high voltage pulsed corona electrical discharge advanced oxidation processes (AOPs) were applied to bleach and degrade C.I. Reactive Green 8 and C.I. Reactive Red 45 organic dyes in water solutions. Two types of hybrid gas/liquid high voltage electrical discharge (corona) reactors, known as hybrid series and hybrid parallel were studied. The difference between these reactors relates to electrode configuration, which affects the amounts of ozone, hydrogen peroxide and hydroxyl radicals produced. Experiments were conducted using dye concentrations of 20 mgl(-1) and 75 mgl(-1), with and without NH4ZSM5 zeolite addition in order to determine possible effects of added solid particles to total process efficiency. The role of ozone in combination with zeolites was assessed through comparative direct ozonation experiments with ozone supplied by an ozone generator. UV/VIS spectrophotometric measurements and measurements of total organic carbon (TOC) were used for the determination of decolorization and mineralization rates.

Biodecolorization of Reactive Yellow-2 by Serratia sp. RN34 Isolated from Textile Wastewater.

PubMed

Najme, Rabia; Hussain, Sabir; Maqbool, Zahid; Imran, Muhammad; Mahmood, Faisal; Manzoor, Hamid; Yasmeen, Tahira; Shehzad, Tanvir

2015-12-01

Remediation of colored textile wastewaters is a matter of interest. In this study, 49 bacteria were isolated from the textile wastewater and tested for their ability to decolorize reactive yellow-2 (RY2) dye. The most efficient isolate, RN34, was identified through amplification, sequencing, and phylogenetic analysis of its 16S rDNA and was designated as Serratia sp. RN34. This bacterium was also found capable of decolorizing other related reactive azo-dyes, including reactive black-5, reactive red-120, and reactive orange-16 but at varying rates. The optimum pH for decolorization of RY2 by the strain RN34 was 7.5 using yeast extract as cosubstrate under static incubation at 30 °C. The strain RN34 also showed potential to decolorize RY2 in the presence of considerable amounts of hexavalent chromium and sodium chloride. A phytotoxicity study demonstrated relatively reduced toxicity of RY2 decolorized products on Vigna radiata plant as compared to the uninoculated RY2 solution.

Studies on the interference by haemoglobin in the determination of bilirubin.

PubMed

van der Woerd-de Lange, J A; Guder, W G; Schleicher, E; Paetzke, I; Schleithoff, M; Wieland, O H

1983-07-01

Haemoglobin interference in the determination of bilirubin was compared in 7 different methods using the Jendrassik-Grof procedure, the Jendrassik-Grof-Nosslin modification, and the more recent procedures using nitrophenyldiazonium, 2,5-dichlorophenyldiazonium, 2,4-dichloraniline, and a direct reading method. To a variable degree, haemoglobin decreased the apparent absorption of the reaction product in all procedures. The extent of this decrease depended on the reagent used, the wavelength, incubation time, bilirubin concentration and the type of blank used. In an attempt to elucidate the mechanism of interference, haemoglobin was found to destroy the bilirubin diazo-compound whereas haemoglobin was ineffective. Likewise, storage of haemolytic samples for several days led to a disappearance of haemoglobin. H2O2, which had no effect in the absence of haemoglobin, potentiated the action of haemoglobin on diazobilirubin coupling. From our observations it can be concluded that haemoglobin disturbs the diazo-bilirubin reaction by a dual mechanism. H2O2, formed from oxyhaemoglobin by autoxidation, destroys the diazo bilirubin colour. In accordance with this explanation, potassium iodide stabilized the diazo compound against the peroxidative effect of oxyhaemoglobin; stabilization was not effective with superoxide dismutase, mannitol or ascorbate.

The composition dependence of the photochemical reactivity of strontium barium titanate

NASA Astrophysics Data System (ADS)

Bhardwaj, Abhilasha

The efficiency of particulate water photolysis catalysts is impractically low due to the recombination of intermediate species and charge carriers. The back reaction can occur easily if the oxidation and reduction sites on the surface of the catalyst are not far enough apart. It is hypothesized that it will be possible to increase the separation of the sites of the two half reactions and reduce the recombination of photogenerated charge carriers by using a ferroelectric material with permanent internal dipolar fields. This separation of the reaction sites may significantly increase the efficiency of the process. The present work compares the photochemical reactivities of ferroelectric and nonferroelectric materials (SrxBa1-xTiO 3, 0.0≤ x ≤1.0) with similar composition and structure. The reactivities are compared by measuring the color change of methylene blue dye after the aqueous dye solution reacts on the surface of ceramic sample pellets as a result of exposure to UV light. The reactivities are also compared by measuring the amount of silver that is formed when an aqueous AgNO3 solution photochemically reacts on the surface. The change in the color of the dye is measured by diffuse reflectance spectroscopy and absorbance measurements. The amount of silver is measured by atomic force microscopy. The photochemical reactivity of SrxBa1-xTiO3 shows a local maximum at the composition of the ferroelectric to non-ferroelectric transition. Also, the reactivities decrease as BaTiO3 and SrTiO3 become less pure. The dominant factors causing this trend in reactivities of SrxBa1-xTiO3 are the dielectric constant and alloy scattering. It is found that higher values of the dielectric constant increase the photochemical reactivity by enlarging the space charge region. The increase in alloy scattering in SrxBa1-xTiO 3 solid solutions as x increases from zero or decreases from 1, has adverse effect on reactivity. There are other factors such as ferroelectric polarization, relative band edge positions and pH of the solution that can influence the reactivity. However, these factors are not significant in determining the composition dependence of the photochemical reactivity of SrxBa 1-xTiO3. The comparison of the surfaces of SrxBa 1-xTiO3 samples imaged by AFM after reaction (with silver nitrate) also showed that the mode of reaction gradually changes from spatially selective reactivity for BaTiO3 to spatially uniform reactivity for SrTiO3. The spatially selective reactivity disappears completely when x in SrxBa1-xTiO3 is greater than or equal to 0.28. The mechanism of the photochemical reaction of methylene blue dye on SrxBa1-xTiO3 was also studied. It is found that the dye reacts by a mechanism similar to that of silver. The methylene blue dye and silver reduce on the surfaces of positively charged domains and the reduced reaction products remain at the reduction reaction site. Extensions of this research would be to experimentally determine the band edges and defect concentrations in SrxBa1-xTiO 3 to get a better understanding of their influence on photochemical reactivity. Since the long term goal of this research is to find a efficient particulate catalyst for photocatalysis of water, the next step in this research is to carry out the photocatalysis of water using SrxBa1-x TiO3 powders. The effect of catalyst particle size should also be analyzed.

Triazine dyes are agonists of the NAADP receptor

PubMed Central

Billington, Richard A; Bak, Judit; Martinez-Coscolla, Ana; Debidda, Marcella; Genazzani, Armando A

2004-01-01

NAADP has been shown to be a potent calcium-releasing second messenger in a wide variety of cell types to date. However, research has been hampered by a lack of pharmacological agents, with which to investigate NAADP-induced calcium release, and by the molecular identity of its cellular target protein being unknown.In the present paper, the sea urchin egg model was used to investigate whether triazine dyes, which can act as nucleotide mimetics, can bind to the NAADP receptor, induce Ca2+ release and be used for affinity chromatography of the receptor.Indeed, all the triazine dyes tested (Reactive Red 120 (RR120), Reactive Green 19 (RG19), Reactive Green 5 (RG5), Cibacron Blue 3GA and Reactive Yellow 86) displayed micromolar affinities, except for Reactive Orange 14. Furthermore, unlike NAADP, RR120, RG19 and RG5 did not bind in an irreversible manner.The compound that displayed the highest affinity, RR120, was tested in a 45Ca2+ efflux assay. This compound released Ca2+ via the NAADP receptor, as shown by the ability of subthreshold NAADP concentrations to inhibit this release. Furthermore, heparin and ruthenium red were unable to block RR120-induced Ca2+ release.We have also shown that RG5 and RG19, immobilised on resins, retain the ability to bind to the receptor, and that this interaction can be disrupted by high salt concentrations. As a proof of principle, we have shown that this can be used to partially purify the NAADP receptor by at least 75-fold.In conclusion, triazine dyes interact with the NAADP receptor, and this could be exploited in future to create a new generation of pharmacological tools to investigate this messenger and, in combination with other techniques, to purify the receptor. PMID:15265807

RhII -Catalyzed β-C(sp2 )-H Alkylation of Enol Ethers, Enamides and Enecarbamates with α-Diazo Dicarbonyl Compounds.

PubMed

McLarney, Brett D; Cavitt, Marchello A; Donnell, Theodore M; Musaev, Djamaladdin G; France, Stefan

2017-01-23

A Rh II -catalyzed method for intermolecular alkylation of the β-C(sp 2 )-H bond of enol ethers, enamides, and enecarbamates with α-diazo-1,3-dicarbonyl compounds is reported. The products are formed in up to 99 % yield and can be readily derivatized under a variety of conditions. By utilizing a combination of experimental and computational studies, the presumptive addition-elimination reaction mechanism was investigated and found to proceed under thermodynamic control at higher temperature. The acquired fundamental knowledge was translated into a strategic reaction design and yielded the first example of the β-C-H functionalizations of acyclic enol ethers using α-diazo-1,3-dicarbonyl compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Elusive Palladium-Diazo Adduct Captured: Synthesis, Isolation and Structural Characterization of [(ArNHC-PPh2 )Pd(η2 -N2 C(Ph)CO2 Et)].

PubMed

Rull, Silvia G; Álvarez, Eleuterio; Fructos, Manuel R; Belderrain, Tomás R; Pérez, Pedro J

2017-06-07

The first example of a diazo palladium adduct is reported. The complexes [(ArNHC-PPh 2 )M(η 2 -N 2 C(Ph)CO 2 Et)] (M=Ni, 3; M=Pd, 4; ArNHC-PPh 2 =3-(2,6-diisopropylphenyl)-1-[(diphenylphosphino)ethyl]imidazol-2-ylidene) were prepared by ligand exchange with styrene-coordinated precursors [(ArNHC-PPh 2 )M(styrene)] (M=Ni, 1; M=Pd, 2). Complex 4 was fully characterized, including X-ray analyses; this constitutes the first example of a diazo adduct compound with palladium, thereby closing the gap between Groups 8 and 10 regarding this type of compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mineralization of hetero bi-functional reactive dye in aqueous solution by Fenton and photo-Fenton reactions.

PubMed

Torrades, Francesc; García-Hortal, José Antonio; García-Montaño, Julia

2015-01-01

This study focused on the advanced oxidation of the hetero bi-functional reactive dye Sumifix Supra Yellow 3RF (CI Reactive Yellow 145) using dark Fenton and photo-Fenton conditions in a lab-scale experiment. A 2(3) factorial design was used to evaluate the effects of the three key factors: temperature, Fe(II) and H2O2 concentrations, for a dye concentration of 250 mg L(-1) with chemical oxygen demand (COD) of 172 mg L(-1) O2 at pH=3. The response function was the COD reduction. This methodology lets us find the effects and interactions of the studied variables and their roles in the efficiency of the treatment process. In the optimization, the correlation coefficients for the model (R2) were 0.948 and 0.965 for Fenton and photo-Fenton treatments, respectively. Under optimized reaction conditions: pH=3, temperature=298 K, [H2O2]=11.765 mM and [Fe(II)]=1.075 mM; 60 min of treatment resulted in a 79% and 92.2% decrease in COD, for the dye taken as the model organic compound, after Fenton and photo-Fenton treatments, respectively.

Combination of photocatalytic and membrane distillation hybrid processes for reactive dyes treatment.

PubMed

Yatmaz, H Cengiz; Dizge, Nadir; Kurt, Merve Sezen

2017-11-01

In this study, the degradation of azo dye solutions (Reactive Red 180 and Reactive Orange 16) of textile industry wastewater was investigated for using innovative hybrid process of photocatalytic and membrane distillation (MD) processes. Photocatalytic oxidation was conducted with semiconductor catalysts (ZnO and TiO2) and their mixture under UVA and UVC irradiation. More effective results were obtained under UVA at the initial stages of the reactions for both dye solutions. ZnO and TiO2 catalysts have given similar efficient results, but results with ZnO were better at initial stages. For the next stage, hybrid design of MD and photocatalytic processes was performed sequentially. Initially, the photocatalytic process was conducted for at least 1 h at initial values of 100 mg/L RR-180 dye solutions and 1 g/L ZnO catalyst loading under UVA irradiation and then treated solution was run through the distillation module at different temperatures (30°C and 40°C) and flow rates (210, 425, and 665 mL/min). Three types of membranes (polypropylene, polytetrafluoroethylene, and polyvinylidene fluoride) with different pore sizes (0.45 and 0.22 μm) were used in the module. Increasing temperature on the side of treated solution and decreasing the temperature on the other side has increased the distillate efficiency.

Resonance Raman and UV-visible spectroscopy of black dyes on textiles.

PubMed

Abbott, Laurence C; Batchelor, Stephen N; Smith, John R Lindsay; Moore, John N

2010-10-10

Resonance Raman and UV-visible diffuse reflectance spectra were recorded from samples of cotton, viscose, polyester, nylon, and acrylic textile swatches dyed black with one of seven single dyes, a mixture of two dyes, or one of seven mixtures of three dyes. The samples generally gave characteristic Raman spectra of the dyes, demonstrating that the technique is applicable for the forensic analysis of dyed black textiles. Survey studies of the widely used dye Reactive Black 5 show that essentially the same Raman spectrum is obtained on bulk sampling from the dye in solution, on viscose, on cotton at different uptakes, and on microscope sampling from the dye in cotton threads and single fibres. The effects of laser irradiation on the Raman bands and emission backgrounds from textile samples with and without dye are also reported. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Determination of minimum enzymatic decolorization time of reactive dye solution by spectroscopic & mathematical approach.

PubMed

Celebi, Mithat; Ozdemir, Zafer Omer; Eroglu, Emre; Altikatoglu, Melda; Guney, Ibrahim

2015-02-01

Synthetic dyes are very important for textile dyeing, paper printing, color photography and petroleum products. Traditional methods of dye removal include biodegradation, precipitation, adsorption, chemical degradation, photo degradation, and chemical coagulation. Dye decolorization with enzymatic reaction is an important issue for several research field (chemistry, environment) In this study, minimum decolorization time of Remazol Brilliant Blue R dye with Horseradish peroxidase enzyme was calculated using with mathematical equation depending on experimental data. Dye decolorization was determined by monitoring the absorbance decrease at the specific maximum wavelength for dye. All experiments were carried out with different initial dye concentrations of Remazol Brilliant Blue R at 25 degrees C constant temperature for 30 minutes. The development of the least squares estimators for a nonlinear model brings about complications not encountered in the case of the linear model. Decolorization times for completely removal of dye were calculated according to equation. It was shown that mathematical equation was conformed exponential curve for dye degradation.

Rapid Asymmetric Synthesis of Disubstituted Allenes by Coupling of Flow‐Generated Diazo Compounds and Propargylated Amines

PubMed Central

Poh, Jian‐Siang; Makai, Szabolcs; von Keutz, Timo; Tran, Duc N.; Battilocchio, Claudio; Pasau, Patrick

2017-01-01

Abstract We report herein the asymmetric coupling of flow‐generated unstabilized diazo compounds and propargylated amine derivatives, using a new pyridinebis(imidazoline) ligand, a copper catalyst and base. The reaction proceeds rapidly, generating chiral allenes in 10–20 minutes with high enantioselectivity (89–98 % de/ee), moderate yields and a wide functional group tolerance. PMID:28075518

Decolorization of a reactive copper-phthalocyanine dye under methanogenic conditions.

PubMed

Beydili, M I; Matthews, R D; Pavlostathis, S G

2001-01-01

The objective of this research was to assess the biological decolorization of the copper-phthalocyanine dye Reactive Blue 7 (RB7) under methanogenic conditions using a mixed, methanogenic culture in a repetitive dye addition batch assay. The initial rate of decolorization was 13.2 mg/L-d and 5.7 mg/L-d for the first and second dye addition, respectively. For an initial RB7 concentration of ca. 300 mg/L, the extent of decolorization remained constant (about 62%) for each repetitive RB7 addition and resulted in a residual color build up. Declining absorbance ratio values (A664/A620) with increasing incubation time confirmed that the observed color removal was due to transformation as opposed to adsorption on the biomass. Chemical decolorization assays using sodium dithionite as the reducing agent resulted in similar absorbance spectra to that obtained after biological decolorization. In addition, in both the chemical and biological decolorization assays, partial oxidation of the reduced dye solution upon exposure to air resulted in higher residual color, indicating that the reduction and decolorization of RB7 are partially reversible. These results also suggest that RB7 reduction and decolorization both chemically and biologically most likely followed a similar reduction mechanism.

Demonstration and Validation of a Fractured Rock Passive Flux Meter

DTIC Science & Technology

2015-04-01

impregnated with a visible dye . The core inflates separately from the two end packers to provide a mechanism for holding the one or ES-2 more reactive...typically 1 meter). Deploying the FRPFM in a borehole and exposing it to flowing groundwater for duration t [T] gradually leaches visible dyes and...tracers from the internal and external sorbent layers and produces residual dye and tracer distributions. Visual inspection of the external layer

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution.

PubMed

Carneiro, Patricia A; Osugi, Marly E; Fugivara, Cecílio S; Boralle, Nivaldo; Furlan, Maysa; B Zanoni, Maria Valnice

2005-04-01

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.

ELUCIDATING THE ROLE OF ELECTRON TRANSFER MEDIATORS IN REDUCTIVE TRANSFORMATIONS IN NATURAL SEDIMENTS

EPA Science Inventory

To study the identity and reactivity of electron transfer mediators (ETMs) in natural sediments, the reduction kinetics of a glass bead-azo dye complex were measured in abiotic and biotic model systems, as well as in natural sediments. In abiotic model systems, the bead-dye comp...

Convenient Microscale Synthesis of a Coumarin Laser Dye Analog

ERIC Educational Resources Information Center

Aktoudianakis, Evangelos; Dicks, Andrew P.

2006-01-01

Coumarin (2H-1-benzopyran-2-one) and its derivatives constitute a fascinating class of organic substances that are utilized industrially in areas such as cosmetics, food preservatives, insecticides and fluorescent laser dyes. The product can be synthesized, purified, and characterized within two hours with benefits of microscale reactivity being…

Assessment on the decolourization of textile dye (Reactive Yellow) using Pseudomonas sp. immobilized on fly ash: Response surface methodology optimization and toxicity evaluation.

PubMed

Roy, Uttariya; Sengupta, Shubhalakshmi; Banerjee, Priya; Das, Papita; Bhowal, Avijit; Datta, Siddhartha

2018-06-18

This study focuses on the investigation of removal of textile dye (Reactive Yellow) by a combined approach of sorption integrated with biodegradation using low cost adsorbent fly ash immobilized with Pseudomonas sp. To ensure immobilization of bacterial species on treated fly ash, fly ash with immobilized bacterial cells was characterized using Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and fluorescence microscopy. Comparative batch studies were carried out using Pseudomonas sp, fly ash and immobilized Pseudomonas sp on flyash and were observed that immobilized Pseudomonas sp on flyash acted as better decolourizing agent. The optimized pH, temperature, and immobilized adsorbent dosage for highest percentage of dye removal were observed to be pH 6, 303 K, 1.2 g/L in all the cases. At optimum condition, the highest percentage of dye removal was found to be 88.51%, 92.62% and 98.72% for sorption (flyash), biodegradation (Pseudomonas sp) and integral approach (Pseudomonas sp on flyash) respectively. Optimization of operating parameters of textile dye decolourization was done by response surface methodology (RSM) using Design Expert 7 software. Phytotoxicity evaluation with Cicer arietinum revealed that seeds exposed to untreated dye effluents showed considerably lower growth, inhibited biochemical, and enzyme parameters with compared to those exposed to treated textile effluents. Thus this immobilized inexpensive technique could be used for removal of synthetic dyes present in textile wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Color removal from dye-containing wastewater by magnesium chloride.

PubMed

Gao, Bao-Yu; Yue, Qin-Yan; Wang, Yan; Zhou, Wei-Zhi

2007-01-01

Color removal by MgCl(2) when treating synthetic waste containing pure dyes was studied. The color removal efficiency of MgCl(2)/Ca(OH)(2) was compared with that of Al(2)(SO(4))(3), polyaluminum chloride (PAC) and FeSO(4)/Ca(OH)(2). The mechanism of color removal by MgCl(2) was also investigated. The experimental results show that the color removal efficiency of MgCl(2) is related to the type of dye and depends on the pH of the waste and the dosage of the coagulants used. Treatment of waste containing reactive dye or dispersed dye with MgCl(2) yielded an optimum color removal ratio when the pH of the solution was equal to or above 12.0. For both the reactive and dispersed dye waste, MgCl(2)/Ca(OH)(2) was shown to be superior to MgCl(2)/NaOH, Al(2)(SO(4))(3), PAC and FeSO(4)/Ca(OH)(2) for color removal. A magnesium hydroxide precipitate formed at pH values greater than 12.0, which provided a large adsorptive surface area and a positive electrostatic surface charge, enabling it to remove the dyes through charge neutralization and an adsorptive coagulating mechanism. So, the MgCl(2)/Ca(OH)(2) system is a viable alternative to some of the more conventional forms of chemical treatment, especially for treating actual textile waste with high natural pH.

Use of sugarcane molasses by Pycnoporus sanguineus for the production of laccase for dye decolorization.

PubMed

Marim, R A; Oliveira, A C C; Marquezoni, R S; Servantes, J P R; Cardoso, B K; Linde, G A; Colauto, N B; Valle, J S

2016-10-17

Pycnoporus sanguineus is a white-rot basidiomycete that produces laccase as the only oxidoreductase; enzyme synthesis depends on cultivation variables, and fungal species and strain. Laccases have wide substrate specificity, oxidize a broad range of compounds, and show potential for use in dye decolorization. We evaluated laccase production in a recently isolated strain of P. sanguineus cultivated with sugarcane molasses as the only carbon source, and urea or yeast extract as the nitrogen source [at various nitrogen concentrations (0.4, 1.4, 2.4, 3.4, and 4.4 g/L)], supplemented with copper (0, 150, 200, 250, and 300 µM), with or without agitation. The enzymatic extract produced at laccase peak activity was tested for dye decolorization capability on Remazol Brilliant Blue R, Reactive Black 5, Reactive Red 195, and Reactive Yellow 145. The nitrogen source did not affect enzyme production and the higher nitrogen concentration (3.4 g/L nitrogen as urea) increased enzymatic activity. The addition of up to 300 µM of Cu did not affect laccase production, whereas cultivation with agitation increased the activity peak by 17%. The highest laccase activity was ~50,000 U/L on the ninth day of cultivation. After 24 h, decolorization was 80% for Remazol Brilliant Blue R, 9% for Reactive Yellow 145, 6% for Reactive Red 195, and 2% for Reactive Black 5. The enzymatic extract of P. sanguineus provides a potential alternative to wastewater treatment. A better understanding of the behavior of this fungus under various culture conditions would allow improvement of the enzyme production bioprocess.

Rapid Asymmetric Synthesis of Disubstituted Allenes by Coupling of Flow-Generated Diazo Compounds and Propargylated Amines.

PubMed

Poh, Jian-Siang; Makai, Szabolcs; von Keutz, Timo; Tran, Duc N; Battilocchio, Claudio; Pasau, Patrick; Ley, Steven V

2017-02-06

We report herein the asymmetric coupling of flow-generated unstabilized diazo compounds and propargylated amine derivatives, using a new pyridinebis(imidazoline) ligand, a copper catalyst and base. The reaction proceeds rapidly, generating chiral allenes in 10-20 minutes with high enantioselectivity (89-98 % de/ee), moderate yields and a wide functional group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction of Diazo Compounds with Difluorocarbene: An Efficient Approach towards 1,1-Difluoroolefins.

PubMed

Zhang, Zhikun; Yu, Weizhi; Wu, Chenggui; Wang, Chengpeng; Zhang, Yan; Wang, Jianbo

2016-01-04

A transition-metal-free difluoromethylenation of diazo compounds that proceeds under mild conditions has been developed and is based on the use of TMSCF2 Br as the difluoromethylene source and tetrabutylammonium bromide (TBAB) as the promoter. The chemoselective formal carbene dimerization reaction is achieved owing to the electronic properties and the relative stability of the difluorocarbene intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-step azide introduction in proteins via an aqueous diazo transfer.

PubMed

van Dongen, Stijn F M; Teeuwen, Rosalie L M; Nallani, Madhavan; van Berkel, Sander S; Cornelissen, Jeroen J L M; Nolte, Roeland J M; van Hest, Jan C M

2009-01-01

The controlled introduction of azides in proteins provides targetable handles for selective protein manipulation. We present here an efficient diazo transfer protocol that can be applied in an aqueous solution, leading to the facile introduction of azides in the side chains of lysine residues and at the N-terminus of enzymes, e.g. horseradish peroxidase (HRP) and the red fluorescent protein DsRed. The effective introduction of azides was verified by mass spectrometry, after which the azido-proteins were used in Cu(I)-catalyzed [3 + 2] cycloaddition reactions. Azido-HRP retained its catalytic activity after conjugation of a small molecule. This modified protein could also be successfully immobilized on the surface of an acetylene-covered polymersome. Azido-DsRed was coupled to an acetylene-bearing protein allowing it to act as a fluorescent label, demonstrating the wide applicability of the diazo transfer procedure.

The state of the art of conventional flow visualization techniques for wind tunnel testing

NASA Technical Reports Server (NTRS)

Settles, G. S.

1982-01-01

Conventional wind tunnel flow visualization techniques which consist of surface flow methods, tracers, and optical methods are presented. Different surface flow methods are outlined: (1) liquid films (oil and fluorescent dye and UV lighting, renewable film via porous dispenser in model, volatile carrier fluid, cryogenic colored oil dots, oil film interferometry); (2) reactive surface treatment (reactive gas injection, reversible dye); (3) transition and heat transfer detectors (evaporation, sublimation, liquid crystals, phase change paints, IR thermography); and (4) tufts (fluorescent mini tufts, cryogenic suitability). Other methods are smoke wire techniques, vapor screens, and optical methods.

Adsorption of C.I. Reactive Red 228 and Congo Red dye from aqueous solution by amino-functionalized Fe3O4 particles: kinetics, equilibrium, and thermodynamics.

PubMed

Yan, Ting-guo; Wang, Li-Juan

2014-01-01

A magnetic adsorbent was synthesized by γ-aminopropyltriethoxysilane (APTES) modification of Fe(3)O(4) particles using a two-step process. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and vibration sample magnetometry were used to characterize the obtained magnetic adsorbent. EDS and XPS showed that APTES polymer was successfully introduced onto the as-prepared Fe(3)O(4)/APTES particle surfaces. The saturation magnetization of the magnetic adsorbent was around 65 emu g(-1), which indicated that the dye can be removed fast and efficiently from aqueous solution with an external magnetic field. The maximum adsorption capacities of Fe(3)O(4)/APTES for C.I. Reactive Red 228 (RR 228) and Congo Red (CR) were 51.4 and 118.8 mg g(-1), respectively. The adsorption of C.I. Reactive Red 228 (RR 228) and Congo Red (CR) on Fe(3)O(4)/APTES particles corresponded well to the Langmuir model and the Freundlich model, respectively. The adsorption processes for RR 228 and CR followed the pseudo-second-order model. The Boyd's film-diffusion model showed that film diffusion also played a major role in the studied adsorption processes for both dyes. Thermodynamic study indicated that both of the adsorption processes of the two dyes are spontaneous exothermic.

Photophysical investigations of squaraine and cyanine dyes and their interaction with bovine serum albumin

NASA Astrophysics Data System (ADS)

Saikiran, M.; Sato, D.; Pandey, S. S.; Kato, T.

2016-04-01

A model far-red sensitive symmetrical squaraine dye (SQ-3) and unsymmetrical near infra-red sensitive cyanine dye (UCD-1) bearing direct-COOH functionalized indole ring were synthesized, characterized and subjected to photophysical investigations including their interaction with bovine serum albumin (BSA) as a model protein in phosphate buffer solution (PBS). Both of the dyes exhibit strong interaction with BSA in phosphate buffer with high apparent binding constant. A judicious tuning of hydrophobic main backbone with reactive functionality for associative interaction with active site of BSA has been found to be necessary for BSA detection in PBS.

Grafting of aniline derivatives onto chitosan and their applications for removal of reactive dyes from industrial effluents.

PubMed

Abbasian, Mojtaba; Jaymand, Mehdi; Niroomand, Pouneh; Farnoudian-Habibi, Amir; Karaj-Abad, Saber Ghasemi

2017-02-01

A series of chitosan-grafted polyaniline derivatives {chitosan-g-polyaniline (CS-g-PANI), chitosan-g-poly(N-methylaniline) (CS-g-PNMANI), and chitosan-g-poly(N-ethylaniline) (CS-g-PNEANI)} were synthesized by in situ chemical oxidation polymerization method. The synthesized copolymers were analyzed by means of Fourier transform infrared (FTIR), and ultraviolet-visible (UV-vis) spectroscopies, thermogravimetric analysis (TGA), and field emission scanning electron microscopy (FE-SEM). These copolymers were applied as adsorbent for removal of acid red 4 (AR4) and direct red 23 (DR23) from aqueous solutions. The adsorption processes were optimized in terms of pH, adsorbent amount, and dyes concentrations. The maximum adsorption capacities (Q m ) for the synthesized copolymers were calculated, and among them the CS-g-PNEANI sample showed highest Q m for both AR4 (98mgg -1 ) and DR23 (112mgg -1 ) dyes. The adsorption kinetics of AR4 and DR23 dyes follow the pseudo-second order kinetic model. The regeneration and reusability tests revealed that the synthesized adsorbents had the relatively good reusability after five repetitions of the adsorption-desorption cycles. As the results, it is expected that the CS-g-PANIs find application for removal of reactive dyes (especially anionic dyes) from industrial effluents mainly due to their low production costs and high adsorption effectiveness. Copyright © 2016 Elsevier B.V. All rights reserved.

New detection targets for amyloid-reactive probes: spectroscopic recognition of bacterial spores

NASA Astrophysics Data System (ADS)

Jones, Guilford, II; Landsman, Pavel

2005-05-01

We report characteristic changes in fluorescence of amyloid-binding dyes Thioflavin T (TfT), pinacyanol (PIN) and related dyes, caused by their interaction with suspended Bacillus spore cultures (B. subtilis, B thuringiensis). The gain in TfT emission in the presence of spores allowed their immediate detection in aqueous suspensions, with a sensitivity limit of < 105 spores per ml. The spectroscopic signatures are consistent with a large number of binding sites for the two dyes on spore coats. The possible structural relationship of these dye binding loci with characteristic motifs (β-stacks) of amyloid deposits and other misfolded protein formations suggests new designs for probing biocontamination and also for clinical studies of non-microbial human pathogens (e.g., amyloid-related protein aggregates in prion-related transmissible encephalopathies or in Alzheimer's disease). Also reported is a special screening technique that was designed and used herein for calibration of new detection probes and assays for spore detection. It employed spectroscopic interactions between the candidate amyloid stains and poly(vinylpyrrolidone)-coated colloid silica (Percoll) nanoparticles that also display remarkable parallelism with the corresponding dye-amyloid and dye-spore reactivities. Percoll may thus find new applications as a convenient non-biological structural model mimicking the putative probe-targeted motifs in both classes of bioanalytes. These findings are important in the design of new probes and assays for important human pathogens (i.e. bacterial spores and amyloidogenic protein aggregates).

Stereoselective Synthesis of Tetrahydroindolizines through the Catalytic Formation of Pyridinium Ylides from Diazo Compounds.

PubMed

Day, Jonathan; McKeever-Abbas, Ben; Dowden, James

2016-05-04

Commercially available iron(III) and copper(I) complexes catalyzed multicomponent cycloaddition reactions between diazo compounds, pyridines, and electrophilic alkenes to give alkaloid-inspired tetrahydroindolizidines in high yield with high diastereoselectivity. Hitherto, the catalytic formation of versatile pyridinium ylides from metal carbenes has been poorly developed; the broad utility demonstrated herein sets the stage for the invention of further multicomponent reactions in future. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simplification and improvement of protein detection in two-dimensional electrophoresis gels with SERVA HPE™ lightning red.

PubMed

Griebel, Anja; Obermaier, Christian; Westermeier, Reiner; Moche, Martin; Büttner, Knut

2013-07-01

A new fluorescent amino-reactive dye has been tested for both labelling proteins prior to electrophoretic separations and between the two steps of two-dimensional electrophoresis. A series of experiments showed, that the labelling of lysines with this dye is compatible with all standard additives used for sample preparation, including reducing substances and carrier ampholytes. Using this dye for pre-labelling considerably simplifies the electrophoresis and detection workflow and provides highly sensitive and quantitative visualisation of proteins.

Novel, one-step synthesis of zwitterionic polymer nanoparticles via distillation-precipitation polymerization and its application for dye removal membrane.

PubMed

Ibrahim, G P Syed; Isloor, Arun M; Inamuddin; Asiri, Abdullah M; Ismail, Norafiqah; Ismail, Ahmed Fauzi; Ashraf, Ghulam Md

2017-11-21

In this work, poly(MBAAm-co-SBMA) zwitterionic polymer nanoparticles were synthesized in one-step via distillation-precipitation polymerization (DPP) and were characterized. [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) as monomer and N, N'-methylene bis(acrylamide) (MBAAm) as cross-linker are used for the synthesis of nanoparticles. As  far as our knowledge, this is the first such report on the synthesis of poly(MBAAm-co-SBMA) nanoparticles via DPP. The newly synthesized nanoparticles were further employed for the surface modification of polysulfone (PSF) hollow fiber membranes for dye removal. The modified hollow fiber membrane exhibited the improved permeability (56 L/ m 2 h bar) and dye removal (>98% of Reactive Black 5 and >80.7% of Reactive orange 16) with the high permeation of salts. Therefore, the as-prepared membrane can have potential application in textile and industrial wastewater treatment.

Comparative study of UV/TiO2, UV/ZnO and photo-Fenton processes for the organic reactive dye degradation in aqueous solution.

PubMed

Peternel, Igor T; Koprivanac, Natalija; Bozić, Ana M Loncarić; Kusić, Hrvoje M

2007-09-05

In this study advanced oxidation processes (AOPs), UV/TiO(2), UV/ZnO and photo-Fenton, were applied in order to degrade C.I. Reactive Red 45 (RR45) dye in aqueous solution. The effects of key operating parameters, such as initial pH, catalyst and hydrogen peroxide dosage as well as the effect of initial dye concentration on decolorization and mineralization extents were studied. Primary objective was to determine the optimal conditions for each of the processes. The influence of added zeolite on the process efficiency was also studied. UV/vis spectrophotometric and total organic carbon (TOC) measurements were performed for determination of decolorization and mineralization extents. It has been found that photo-Fenton process was the most efficient with 74.2% TOC removal and complete color removal achieved after a 1h treatment.

Removal of reactive blue 19 dye by sono, photo and sonophotocatalytic oxidation using visible light.

PubMed

Khan, Muhammad Abdul Nasir; Siddique, Maria; Wahid, Fazli; Khan, Romana

2015-09-01

An efficient sonophotocatalytic degradation of reactive blue 19 (RB 19) dye was successfully carried out using sulfur-doped TiO2 (S-TiO2) nanoparticles. The effect of various treatment processes that is sonolysis, photolysis, catalysis, sonocatalysis, photocatalysis, and sonophotocatalysis were investigated for RB 19 removal. S-TiO2 were synthesized in 1, 3 and 5 wt.% of sulfur by sol-gel process and characterized by X-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive X-ray (SEM-EDX), UV-Visible diffuse reflectance spectra (DRS). The results confirm anatase phase of TiO2, porous agglomerate structure, and a red shift in the absorbance spectra of S-TiO2. The dye degradation was studied by using UV-Vis spectrophotometer at λ max=594 nm. The reaction parameters such as pH, catalyst dosage, initial dye concentration, ultrasonic power and effect of sulfur doping in different weight percent were studied to find out the optimum degradation conditions. Optimum conditions were found as: S-TiO2=5 wt.%, catalyst (S-TiO2 5 wt.%)=50mg, RB 19 solution concentration=20 mg L(-1), pH=3, ultrasound power=100 and operating temperature=25°C. The response of 5 wt.% S-TiO2 was found better than 1 and 3 wt.% S-TiO2 and other forms TiO2. The sonophotocatalysis process was superior to other methods. During this process the ultrasound cavitation and photocatalysis water splitting takes place which leads to the generation of OH. As reveled by the GCMS results the reactive blue 19 (20 mg L(-1)) was degraded to 90% within 120 min. The S-TiO2 sonophotocatalysis system was studied for the first time for dye degradation and was found practicable, efficient and cost effective for the degradation of complex and resistant dyes such as RB19. Copyright © 2015. Published by Elsevier B.V.

Decolorization of salt-alkaline effluent with industrial reactive dyes by laccase-producing Basidiomycetes strains.

PubMed

Moreira-Neto, S L; Mussatto, S I; Machado, K M G; Milagres, A M F

2013-04-01

The discharge of highly coloured synthetic dye effluents into rivers and lakes is harmful to the water bodies, and therefore, intensive researches have been focussed on the decolorization of wastewater by biological, physical or chemical treatments. In the present study, 12 basidiomycetes strains from the genus Pleurotus, Trametes, Lentinus, Peniophora, Pycnoporus, Rigidoporus, Hygrocybe and Psilocybe were evaluated for decolorization of the reactive dyes Cibacron Brilliant Blue H-GR and Cibacron Red FN-2BL, both in solid and liquid media. Among the evaluated fungi, seven showed great ability to decolorize the synthetic textile effluent, both in vivo (74-77%) or in vitro (60-74%), and laccase was the main ligninolytic enzyme involved on dyes decolorization. Pleurotus ostreatus, Trametes villosa and Peniophora cinerea reduced near to 60% of the effluent colour after only 1 h of treatment. The decolorization results were still improved by establishing the nitrogen source and amount to be used during the fungal strains cultivation in synthetic medium previous their action on the textile effluent, with yeast extract being a better nitrogen source than ammonium tartarate. These results contribute for the development of an effective microbiological process for decolorization of dye effluents with reduced time of treatment. © 2013 The Society for Applied Microbiology.

Carbonaceous material production from vegetable residue and their use in the removal of textile dyes present in wastewater

NASA Astrophysics Data System (ADS)

Peláez-Cid, A. A.; Tlalpa-Galán, M. A.; Herrera-González, A. M.

2013-06-01

This paper presents the adsorption results of acid, basic, direct, vat, and reactive-type dyes on carbonaceous adsorbent materials prepared starting off vegetable residue such as Opuntia ficus indica and Casimiroa edulis fruit wastes. The adsorbents prepared from Opuntia ficus indica waste were designated: TunaAsh, CarTunaT, and CarTunaQ. The materials obtained from Casimiroa edulis waste were named: CenZAP, CarZAPT, and CarZAPQ. TunaAsh and CenZAP consist of ashes obtained at 550 °C CarTunaT and CarZAPT consist of the materials carbonized at 400 °C lastly, CarTunaQ and CarZAPQ consist of chemically activated carbons using H3PO4 at 400 °C. Only the chemically activated materials were washed with distilled water until a neutral pH was obtained after their carbonization. All materials were ground and sieved to obtain a particle size ranging from 0.25 to 0.84 mm. The static adsorption results showed that both ashes and chemically activated carbon are more efficient at dye removal for both vegetable residues. For TunaAsh and CarTunaQ, removal rates of up to 100% in the cases of basic, acid, and direct dyes were achieved. Regarding wastewater containing reactive dyes, the efficiency ranged from 60 to 100%. For vat effluents, it ranged from 42 to 52%. In the case of CenZAP and CarZAPQ, it was possible to treat reactive effluents with rates ranging between 63 and 91%. Regarding vat effluents, it ranged from 57 to 68%. The process of characterization for all materials was done using scanning electron microscopy and infrared spectroscopy.

2-Diazo-1-(4-hydroxyphenyl)ethanone: A Versatile Photochemical and Synthetic Reagenta

PubMed Central

Senadheera, Sanjeewa N.; Evans, Anthony S.; Toscano, John P.; Givens, Richard S.

2014-01-01

α-Diazo arylketones are well-known substrates for Wolff rearrangement to phenylacetic acids through a ketene intermediate by either thermal or photochemical activation. Likewise, α-substituted p-hydroxyphenacyl (pHP) esters are substrates for photo-Favorskii rerrangements to phenylacetic acids by a different pathway that purportedly involves a cyclopropanone intermediate. In this paper, we show that the photolysis of a series of α-diazo-p-hydroxyacetophenones and p-hydroxyphenacyl (pHP) α-esters both generate the identical rearranged phenylacetates as major products. Since α-diazo-p-hydroxyacetophenone (1a, pHP N2) contains all the necessary functionalities for either Wolff or Favorskii rearrangement, we were prompted to probe this intriguing mechanistic dichotomy under conditions favorable to the photo-Favorskii reangement, i.e., photolysis in hydroxylic media. An investigation of the mechanism for conversion of 1a to p-hydroxyphenyl acetic acid (4a) using time-resolved infrared (TRIR) spectroscopy clearly demonstrates the formation of a ketene intermediate that is subsequently trapped by solvent or nucleophiles. The photoreaction of 1a is quenched by oxygen and sensitized by triplet sensitizers and the quantum yields for 1a–c range from 0.19 to a robust 0.25. The lifetime of the triplet, determined by Stern-Volmer quenching, is 15 ns with a rate for appearance of 4a of k = 7,1 × 106 s−1 in aq. acetonitrile (1:1 v:v). These studies establish that the primary rearrangement pathway for 1a involves ketene formation in accordance with the photo-Wolff rearrangement. Furthermore we have also demonstrated the synthetic utility of 1a as an esterification and etherification reagent with a variety of substituted α-diazo-p-hydroxyacetophenones, using them as synthons for efficiently coupling it to acids and phenols to produce pHP protect substrates. PMID:24305682

2-Diazo-1-(4-hydroxyphenyl)ethanone: a versatile photochemical and synthetic reagent.

PubMed

Senadheera, Sanjeewa N; Evans, Anthony S; Toscano, John P; Givens, Richard S

2014-02-01

α-Diazo arylketones are well-known substrates for Wolff rearrangement to phenylacetic acids through a ketene intermediate by either thermal or photochemical activation. Likewise, α-substituted p-hydroxyphenacyl (pHP) esters are substrates for photo-Favorskii rearrangements to phenylacetic acids by a different pathway that purportedly involves a cyclopropanone intermediate. In this paper, we show that the photolysis of a series of α-diazo-p-hydroxyacetophenones and p-hydroxyphenacyl (pHP) α-esters both generate the identical rearranged phenylacetates as major products. Since α-diazo-p-hydroxyacetophenone (1a, pHP N2) contains all the necessary functionalities for either Wolff or Favorskii rearrangement, we were prompted to probe this intriguing mechanistic dichotomy under conditions favorable to the photo-Favorskii rearrangement, i.e., photolysis in hydroxylic media. An investigation of the mechanism for conversion of 1a to p-hydroxyphenyl acetic acid (4a) using time-resolved infrared (TRIR) spectroscopy clearly demonstrates the formation of a ketene intermediate that is subsequently trapped by solvent or nucleophiles. The photoreaction of 1a is quenched by oxygen and sensitized by triplet sensitizers and the quantum yields for 1a-c range from 0.19 to a robust 0.25. The lifetime of the triplet, determined by Stern-Volmer quenching, is 31 ns with a rate for appearance of 4a of k = 7.1 × 10(6) s(-1) in aq. acetonitrile (1 : 1 v : v). These studies establish that the primary rearrangement pathway for 1a involves ketene formation in accordance with the photo-Wolff rearrangement. Furthermore we have also demonstrated the synthetic utility of 1a as an esterification and etherification reagent with a variety of substituted α-diazo-p-hydroxyacetophenones, using them as synthons for efficiently coupling it to acids and phenols to produce pHP protect substrates.

Preparation of fluorescent-dye-labeled cDNA from RNA for microarray hybridization.

PubMed

Ares, Manuel

2014-01-01

This protocol describes how to prepare fluorescently labeled cDNA for hybridization to microarrays. It consists of two steps: first, a mixture of anchored oligo(dT) and random hexamers is used to prime amine-modified cDNA synthesis by reverse transcriptase using a modified deoxynucleotide with a reactive amine group (aminoallyl-dUTP) and an RNA sample as a template. Second, the cDNA is purified and exchanged into bicarbonate buffer so that the amine groups in the cDNA react with the dye N-hydroxysuccinimide (NHS) esters, covalently joining the dye to the cDNA. The dye-coupled cDNA is purified again, and the amount of dye incorporated per microgram of cDNA is determined.

Decolorizing of azo dye Reactive red 24 aqueous solution using exfoliated graphite and H2O2 under ultrasound irradiation.

PubMed

Li, Mei; Li, Ji-Tai; Sun, Han-Wen

2008-07-01

At its natural pH (6.95), the decolorization of Reactive red 24 in ultrasound, ultrasound/H2O2, exfoliated graphite, ultrasound/exfoliated graphite, exfoliated graphite/H2O2 and ultrasound/exfoliated graphite/H2O2 systems were compared. An enhancement was observed for the decolorization in ultrasound/exfoliated graphite/H2O2 system. The effect of solution pH, H2O2 and exfoliated graphite dosages, and temperature on the decolorization of Reactive red 24 was investigated. The sonochemical treatment in combination with exfoliated graphite/H2O2 showed a synergistic effect for the decolorization of Reactive red 24. The results indicated that under proper conditions, there was a possibility to remove Reactive red 24 very efficient from aqueous solution. The decolorization of other azo dyes (Reactive red 2, Methyl orange, Acid red 1, Acid red 73, Acid red 249, Acid orange 7, Acid blue 113, Acid brown 75, Acid green 20, Acid yellow 42, Acid mordant brown 33, Acid mordant yellow 10 and Direct green 1) was also investigated, at their natural pH.

Reuse of Textile Dyeing Effluents Treated with Coupled Nanofiltration and Electrochemical Processes

PubMed Central

Buscio, Valentina; García-Jiménez, María; Vilaseca, Mercè; López-Grimau, Victor; Crespi, Martí; Gutiérrez-Bouzán, Carmen

2016-01-01

The reactive dye Cibacron Yellow S-3R was selected to evaluate the feasibility of combining nanofiltration membranes with electrochemical processes to treat textile wastewater. Synthetic dyeing effluents were treated by means of two nanofiltration membranes, Hydracore10 and Hydracore50. Up to 98% of dye removal was achieved. The influence of salt concentration and pH on membrane treatment was studied. The best dye removal yield was achieved at pH 3 in the presence of 60 g/L of NaCl. After the membrane filtration, the concentrate containing high dye concentration was treated by means of an electrochemical process at three different current densities: 33, 83, and 166 mA/cm2. Results showed a lineal relationship between treatment time and applied current density. Both permeates and electrochemically-decoloured effluents were reused in new dyeing processes (100% of permeate and 70% of decoloured concentrates). Dyed fabrics were evaluated with respect to original dyeing. Colour differences were found to be into the acceptance range. PMID:28773614

Copper(II)-catalyzed oxidative [3+2] cycloaddition reactions of secondary amines with α-diazo compounds: a facile and efficient synthesis of 1,2,3-triazoles.

PubMed

Li, Yi-Jin; Li, Xue; Zhang, Shao-Xiao; Zhao, Yu-Long; Liu, Qun

2015-07-25

A novel copper-catalyzed [3+2] cycloaddition reaction of secondary amines with α-diazo compounds has been developed via a cross-dehydrogenative coupling process. The reaction involves a sequential aerobic oxidation/[3+2] cycloaddition/oxidative aromatization procedure and provides an efficient method for the construction of 1,2,3-triazoles in a single step in an atom-economic manner from readily available starting materials under very mild conditions.

Potassium N-Iodo p-Toluenesulfonamide (TsNIK, Iodamine-T): A New Reagent for the Oxidation of Hydrazones to Diazo Compounds

PubMed Central

Nicolle, Simon M; Moody, Christopher J

2014-01-01

A new reagent for the oxidation of hydrazones to diazo compounds is described. N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T) allows the preparation of α-diazoesters, α-diazoamides, α-diazoketones and α-diazophosphonates in good yield and in high purity after a simple extractive work-up. α-Diazoesters were also obtained in high yield from the corresponding ketones through a one-pot process of hydrazone formation/oxidation. PMID:24615944

A Versatile Room-Temperature Route to Di- and Trisubstituted Allenes Using Flow-Generated Diazo Compounds.

PubMed

Poh, Jian-Siang; Tran, Duc N; Battilocchio, Claudio; Hawkins, Joel M; Ley, Steven V

2015-06-26

A copper-catalyzed coupling reaction between flow-generated unstabilized diazo compounds and terminal alkynes provides di- and trisubstituted allenes. This extremely mild and rapid transformation is highly tolerant of several functional groups. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Diazo Printing of ERTS Color Composites

NASA Technical Reports Server (NTRS)

Mcmurtry, G. J.; Petersen, G. W. (Principal Investigator); Kowalik, W. S.

1975-01-01

The author has identified the following significant results. ERTS-1 color composites were made with the help of a Diazo developer and printer. Five single channel, density standards were established, using typical ERTS images, in order to determine exposure time. These standards were used to develop a graph from which the exposure time for any transparency can be estimated. Exposure times varied from 3 to 30 minutes, and clear colored polyester sheets from two manufactures were used with slightly different, but equally successful, results.

Preparation of unsymmetrical ketones from tosylhydrazones and aromatic aldehydes via formyl C-H bond insertion.

PubMed

Allwood, Daniel M; Blakemore, David C; Ley, Steven V

2014-06-06

Preparation of ketones by insertion of diazo compounds into the formyl C-H bond of an aldehyde is an attractive procedure, but use of structurally diverse diazo compounds is hampered by preparation and safety issues. A convenient procedure for the synthesis of unsymmetrical ketones from bench-stable tosylhydrazones and aryl aldehydes is reported. The procedure can be performed in one pot from the parent carbonyl compound and needs only a base, with no additional promoters being required.

Photobleachable Diazonium Salt-Phenolic Resin Two-Layer Resist System

NASA Astrophysics Data System (ADS)

Uchino, Shou-ichi; Iwayanagi, Takao; Hashimoto, Michiaki

1988-01-01

This article describes a new negative two-layer photoresist system formed by a simple, successive spin-coating method. An aqueous acetic acid solution of diazonium salt and poly(N-vinylpyrrolidone) is deposited so as to contact a phenolic resin film spin-coated on a silicon wafer. The diazonium salt diffuses into the phenolic resin layer after standing for several minutes. The residual solution on the phenolic resin film doped with diazonium salt is spun to form the diazonium salt-poly(N-vinylpyrrolidone) top layer. This forms a uniform two-layer resist without phase separation or striation. Upon UV exposure, the diazonium salt in the top layer bleaches to act as a CEL dye, while the diazonium salt in the bottom layer decomposes to cause insolubilization. Half μm line-and-space patterns are obtained with an i-line stepper using 4-diazo-N,N-dimethylaniline chloride zinc chloride double salt as the diazonium salt and a cresol novolac resin for the bottom polymer layer. The resist formation processes, insolubilization mechanism, and the resolution capability of the new two-layer resist are discussed.

Liquid-phase separation of reactive dye by wood-rotting fungus: a biotechnological approach.

PubMed

Binupriya, Arthur R; Sathishkumar, Muthuswamy; Dhamodaran, Kavitha; Jayabalan, Rasu; Swaminathan, Krishnaswamy; Yun, Sei Eok

2007-08-01

The live and pretreated mycelial pellets/biomass of Trametes versicolor was used for the biosorption of a textile dye, reactive blue MR (RBMR) from aqueous solution. The parameters that affect the biosorption of RBMR, such as contact time, concentration of dye and pH, on the extent of RBMR adsorption were investigated. To develop an effective and accurate design model for removal of dye, adsorption kinetics and equilibrium data are essential basic requirements. Lagergren first-order, second-order and Bangham's model were used to fit the experimental data. Results of the kinetic studies showed that the second order kinetic model fitted well for the present experimental data. The Langmuir, Freundlich and Temkin adsorption models were used for the mathematical description of the biosorption equilibrium. The biosorption equilibrium data obeyed well for Langmuir isotherm and the maximum adsorption capacities were found to be 49.8, 51.6, 47.4 and 46.7 mg/g for live, autoclaved, acid- and alkali-pretreated biomass. The dye uptake capacity order of the fungal biomass was found as autoclaved > live > acid-treated > alkali-pretreated. The Freundlich and Temkin models were also able to describe the biosorption equilibrium on RBMR on live and pretreated fungal biomass. Acidic pH was favorable for the adsorption of dye. Studies on pH effect and desorption show that chemisorption seems to play a major role in the adsorption process. On comparison with fixed bed adsorption, batch mode adsorption was more efficient in adsorption of RBMR.

A comparative study on decolorization of reactive azo and indigoid dyes by free/immobilized pellets of Trametes versicolor and Funalia trogii.

PubMed

Yildirim, Seval Cing; Yesilada, Ozfer

2015-11-01

The objective of the present study was to investigate decolorization of Acid Blue 74 and Reactive Blue 198 dyes by free and immobilized white rot fungal pellets in order to confirm the possibility of practical application via repeated-batch cultivation. Decolorization studies were conducted using free pellets (FP), fungal cells immobilized on activated carbon (IFCAC) and pinewood (IFCP), and also fungal cells entrapped in alginate beads (FCEAB). No additional nitrogen and carbon source was used and high decolorization rates were achieved in only dye-contained media without pH adjustment. Acid Blue 74 was decolorized 96 and 94% within 2 hr by Trametes versicolor and Funalia trogii free pellets, respectively. These values were 87 and 84% for Reactive Blue 198, in this respect. Immobilization of fungal cells on pinewood increased the usability of pellets and the average decolorization efficiency of both dyes. The micro environment changed in the presence of pinewood and increased the stability of immobilized pellets. Decolorization was performed rapidly and efficiently. Laccase activity enhanced with availability of pinewood, and high laccase production with F. trogii was obtained. After separation by sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE), the molecular weight of T versicolor and F. trogii laccase bands was determined 64 and 61 kDa approximately. Green bands were obtained by the activity staining process with laccase substrate (ABTS) after gel renaturation step.

Decolorization of textile dyes in an air-lift bioreactor inoculated with Bjerkandera adusta OBR105.

PubMed

Sodaneath, Hong; Lee, Jung-In; Yang, Seung-Ok; Jung, Hyekyeng; Ryu, Hee Wook; Cho, Kyung-Suk

2017-09-19

A new decolorizing white-rot fungus, OBR105, was isolated from Mount Odae in South Korea and identified by the morphological characterization of its fruit body and spores and partial 18s rDNA sequences. The ligninolytic enzyme activity of OBR105 was studied to characterize their decolorizing mechanism using a spectrophotometric enzyme assay. For the evaluation of the decolorization capacity of OBR105, the isolate was incubated in an erlenmeyer flask and in an airlifte bioreator with potato dextrose broth (PDB) medium supplemented with each dye. In addition, the decolorization efficiency of real textile wastewater was evaluated in an airlift bioreactor inoculated with the isolate. The isolate was identified as Bjerkandera adusta and had ligninolytic enzymes such as laccase, lignin peroxidase (LiP), and Mn-dependent peroxidase (MnP). Its LiP activity was higher than its MnP and laccase activities. B. adusta OBR105 successfully decolorized reactive dyes (red 120, blue 4, orange 16, and black 5) and acid dyes (red 114, blue 62, orange 7, and black 172). B. adusta OBR105 decolorized 91-99% of 200 mg L -1 of each dye (except acid orange 7) within 3 days in a PDB medium at 28°C, pH 5, and 150 rpm. This fungus decolorized only 45% of 200 mg L -1 acid orange 7 (single azo-type dye) within 3 days, and the decolorization efficiency did not increase by prolonging the cultivation time. In the air-lift bioreactor, B. adusta OBR105 displayed a high decolorization capacity, greater than 90%, for 3 acid dyes (red 114, blue 62, and black 172) and 1 reactive dye (blue 4) within 10-15 h of treatment. B. adusta OBR105 could decolorize real textile wastewater in the air-lift bioreactor. This result suggests that an air-lift reactor employing B. adusta OBR105 is a promising bioreactor for the treatment of dye wastewater.

Production of Superoxide in Bacteria Is Stress- and Cell State-Dependent: A Gating-Optimized Flow Cytometry Method that Minimizes ROS Measurement Artifacts with Fluorescent Dyes.

PubMed

McBee, Megan E; Chionh, Yok H; Sharaf, Mariam L; Ho, Peiying; Cai, Maggie W L; Dedon, Peter C

2017-01-01

The role of reactive oxygen species (ROS) in microbial metabolism and stress response has emerged as a major theme in microbiology and infectious disease. Reactive fluorescent dyes have the potential to advance the study of ROS in the complex intracellular environment, especially for high-content and high-throughput analyses. However, current dye-based approaches to measuring intracellular ROS have the potential for significant artifacts. Here, we describe a robust platform for flow cytometric quantification of ROS in bacteria using fluorescent dyes, with ROS measurements in 10s-of-1000s of individual cells under a variety of conditions. False positives and variability among sample types (e.g., bacterial species, stress conditions) are reduced with a flexible four-step gating scheme that accounts for side- and forward-scattered light (morphological changes), background fluorescence, DNA content, and dye uptake to identify cells producing ROS. Using CellROX Green dye with Escherichia coli, Mycobacterium smegmatis , and Mycobacterium bovis BCG as diverse model bacteria, we show that (1) the generation of a quantifiable CellROX Green signal for superoxide, but not hydrogen peroxide-induced hydroxyl radicals, validates this dye as a superoxide detector; (2) the level of dye-detectable superoxide does not correlate with cytotoxicity or antibiotic sensitivity; (3) the non-replicating, antibiotic tolerant state of nutrient-deprived mycobacteria is associated with high levels of superoxide; and (4) antibiotic-induced production of superoxide is idiosyncratic with regard to both the species and the physiological state of the bacteria. We also show that the gating method is applicable to other fluorescent indicator dyes, such as the 5-carboxyfluorescein diacetate acetoxymethyl ester and 5-cyano-2,3-ditolyl tetrazolium chloride for cellular esterase and reductive respiratory activities, respectively. These results demonstrate that properly controlled flow cytometry coupled with fluorescent probes provides precise and accurate quantitative analysis of ROS generation and metabolic changes in stressed bacteria.

Spectrophotometric Determination of Nitrogen Oxides in the Air with 2-N-Ethyl-5-Naphthol-7-Sulfonic Acid

NASA Astrophysics Data System (ADS)

Huang, Y.; Shi, W.; Zhang, C.; Wen, H.

2017-09-01

For the determination of nitrogen oxides in the air, the structure of diazo and coupling compounds was studied and tested by experiments. The conditions and methods of diazo and coupling reactions were investigated. Furthermore, a spectrophotometric method using sulfanilamide as a diazo compound and 2-N-ethyl-5-naphthol-7-sulfonic acid (N-ethyl J acid) as a coupling compound was proposed. The maximum absorption wavelength of sulfanilamide-Nethyl J acid azo compound was at 478 nm. The molar absorptivity was 4.31 × 104 L/(mol × cm) with a recovery of 98.7-100.9% and RSD of 1.85%. For nitrogen oxides, the determinate limit of this measurement was 0.015 mg/m3 and the determinate range 0.024-2.0 mg/m3. Moreover, a high degree of correlation was observed between the results obtained by the proposed method and the standard methods. The proposed method can be easily applied to determine nitrogen oxides in the air.

Light-Induced C-H Arylation of (Hetero)arenes by In Situ Generated Diazo Anhydrides.

PubMed

Cantillo, David; Mateos, Carlos; Rincon, Juan A; de Frutos, Oscar; Kappe, C Oliver

2015-09-07

Diazo anhydrides (Ar-N=N-O-N=N-Ar) have been known since 1896 but have rarely been used in synthesis. This communication describes the development of a photochemical catalyst-free C-H arylation methodology for the preparation of bi(hetero)aryls by the one-pot reaction of anilines with tert-butyl nitrite and (hetero)arenes under neutral conditions. The key step in this procedure is the in situ formation and subsequent photochemical (>300 nm) homolytic cleavage of a transient diazo anhydride intermediate. The generated aryl radical then efficiently reacts with a (hetero)arene to form the desired bi(hetero)aryls producing only nitrogen, water, and tert-butanol as byproducts. The scope of the reaction for several substituted anilines and (hetero)arenes was investigated. A continuous-flow protocol increasing selectivity and safety has been developed enabling the experimentally straightforward preparation of a variety of substituted bi(hetero)aryls within 45 min of reaction time. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium(III)-Catalyzed ortho-Alkylation of Phenoxy Substrates with Diazo Compounds via C-H Activation: A Case of Decarboxylative Pyrimidine/Pyridine Migratory Cyclization Rather than Removal of Pyrimidine/Pyridine Directing Group.

PubMed

Ravi, Manjula; Allu, Srinivasarao; Swamy, K C Kumara

2017-03-03

An efficient Rh(III)-catalyzed ortho-alkylation of phenoxy substrates with diazo compounds has been achieved for the first time using pyrimidine or pyridine as the directing group. Furthermore, bis-alkylation has also been achieved using para-substituted phenoxypyrimidine and 3 mol equiv of the diazo ester. The ortho-alkylated derivatives of phenoxy products possessing the ester functionality undergo decarboxylative pyrimidine/pyridine migratory cyclization (rather than deprotection of pyrimidine/pyridine group) using 20% NaOEt in EtOH affording a novel class of 3-(pyrimidin-2(1H)-ylidene)benzofuran-2(3H)-ones and 6-methyl-3-(pyridin-2(1H)-ylidene)benzofuran-2(3H)-one. The ortho-alkylated phenoxypyridine possessing ester functionality also undergoes decarboxylative pyridine migratory cyclization using MeOTf/NaOMe in toluene providing 6-methyl-3-(1-methylpyridin-2(1H)-ylidene)benzofuran-2(3H)-one.

A Novel, Diazonium-Phenolic Resin Two-Layer Resist System Utilizing Photoinduced Interfacial Insolubilization

NASA Astrophysics Data System (ADS)

Uchino, Shou-ichi; Iwayanagi, Takao; Ueno, Takumi; Hashimoto, Michiaki; Nonogaki, Saburo

1987-08-01

This paper deals with a negative two-layer photoresist system utilizing a photoinduced insolubilization process at the interface. The bottom layer is a phenolic resin either with or without aromatic azide and the top layer is a photosensitive layer comprised of an aromatic diazonium compound and a water soluble polymer. Upon exposure to light, the diazo compound decomposes to cause insolubilization at the interface between the two layers. The system exhibits high contrast due to the combination of interfacial insolubilization and contrast enhancement by photobleaching of the diazonium compound. Patterns of 0.5 um lines and spaces are obtained using an i-line stepper and a resist system containing 4-diazo-N,N-dimethylaniline chloride zinc chloride in the top layer and 3-(4-azidostyry1)- 5,5-dimethyl- 2-cyclohexen-1-one in the bottom layer. Resists with varying spectral responses from mid-UV to g-line can be designed by selecting the kind of diazo compound used in the top layer.

Fluorescent labeling of proteins with amine-specific 1,3,2-(2H)-dioxaborine polymethine dye.

PubMed

Gerasov, Andriy; Shandura, Mykola; Kovtun, Yuriy; Losytskyy, Mykhaylo; Negrutska, Valentyna; Dubey, Igor

2012-01-15

A novel water-soluble amine-reactive dioxaborine trimethine dye was synthesized in a good yield and characterized. The potential of the dye as a specific reagent for protein labeling was demonstrated with bovine serum albumin and lysozyme. Its interaction with proteins was studied by fluorescence spectroscopy and gel electrophoresis. The covalent binding of this almost nonfluorescent dye to proteins results in a 75- to 78-fold increase of its emission intensity accompanied by a red shift of the fluorescence emission maximum by 27 to 45 nm, with fluorescence wavelengths of labeled biomolecules being more than 600 nm. The dye does not require activation for the labeling reaction and can be used in a variety of bioassay applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Certain tricyclic and pentacyclic-hetero nitrogen rhodol dyes

DOEpatents

Haugland, Richard P.; Whitaker, James E.

1993-01-01

Novel fluorescent dyes based on the rhodol structure are provided. The new reagents contain functional groups capable of forming a stable fluorescent product with functional groups typically found in biomolecules or polymers including amines, phenols, thiols, acids, aldehydes and ketones. Reactive groups in the rhodol dyes include activated esters, isothiocyanates, amines, hydrazines, halides, acids, azides, maleimides, aldehydes, alcohols, acrylamides and haloacetamides. The products are detected by their absorbance or fluorescence properties. The spectral properties of the fluorescent dyes are sufficiently similar in wavelengths and intensity to fluorescein or rhodamine derivatives as to permit use of the same equipment. The dyes, however, show less spectral sensitivity to pH in the physiological range than does fluorescein, have higher solubility in non-polar solvents and have improved photostability and quantum yields.

The performance and decolourization kinetics of O3/H2O2 oxidation of reactive green 19 dye in wastewater

NASA Astrophysics Data System (ADS)

Sabri, S. N.; Abidin, C. Z. A.; Fahmi; Kow, S. H.; Razali, N. A.

2018-03-01

The degradations characteristic of azo dye Reactive Green 19 (RG19) was investigated using advanced oxidation process (AOPs). It was evaluated based on colour and chemical oxygen demand (COD) removal. The effect of operational parameters such as initial dye concentration, initial dosage of hydrogen peroxide (H2O2), contact time, and pH was also being studied. The samples were treated by ozonation (O3) and peroxone O3/H2O2 process. Advanced oxidation processes (AOPs) involve two stages of oxidation; firstly is the formation of strong oxidant and secondly the reaction of organic contaminants in water. In addition, the term advanced oxidation is referring to the processes in which oxidation of organic contaminants occurs primarily through reactions with hydroxyl radicals. There are several analyses that use to determine the efficiency of the treatment process, which are UV-Vis absorption spectra, COD, Fourier Transform Infrared (FT-IR), and pH. The results demonstrated that the ozone oxidation was efficient in decolourization and good in mineralization, based on the reduction of colour and COD. Additionally, results indicate that H2O2 is able to perform better than ozonation in order to decolourize the dye wastewater with 0.5 mL H2O2/L dye dosage of H2O2 at different initial concentration, initial pH, with contact time.

Production and characterization of laccase from Cyathus bulleri and its use in decolourization of recalcitrant textile dyes.

PubMed

Salony; Mishra, S; Bisaria, V S

2006-08-01

Many fungi (particularly the white rot) are well suited for treatment of a broad range of textile dye effluents due to the versatility of the lignin-degrading enzymes produced by them. We have investigated decolourization of a number of recalcitrant reactive azo and acid dyes using the culture filtrate and purified laccase from the fungus Cyathus bulleri. For this, the enzyme was purified from the culture filtrate to a high specific activity of 4,022 IU mg(-1) protein, produced under optimized carbon, nitrogen and C/N ratio with induction by 2,6-dimethylaniline. The protein was characterized as a monomer of 58+/-5.0 kDa with carbohydrate content of 16% and was found to contain all three Cu(II) centres. The three internal peptide sequences showed sequence identity (80-92%) with laccases of a number of white rot fungi. Substrate specificity indicated highest catalytic efficiency (k(cat)/K(M)) on guaiacol followed by 2,2'-azino-bis(3-ethylthiazoline-6-sulfonic acid) (ABTS). Decolourization of a number of reactive azo and acid dyes was seen with the culture filtrate of the fungus containing predominantly laccase. In spite of no observable effect of purified laccase on other dyes, the ability to decolourize these was achieved in the presence of the redox mediator ABTS, with 50% decolourization in 0.5-5.4 days.

Wood and humus decay strategies by white-rot basidiomycetes correlate with two different dye decolorization and enzyme secretion patterns on agar plates.

PubMed

Barrasa, José M; Blanco, María N; Esteve-Raventós, Fernando; Altés, Alberto; Checa, Julia; Martínez, Angel T; Ruiz-Dueñas, Francisco J

2014-11-01

During several forays for ligninolytic fungi in different Spanish native forests, 35 white-rot basidiomycetes growing on dead wood (16 species from 12 genera) and leaf litter (19 species from 10 genera) were selected for their ability to decolorize two recalcitrant aromatic dyes (Reactive Blue 38 and Reactive Black 5) added to malt extract agar medium. In this study, two dye decolorization patterns were observed and correlated with two ecophysiological groups (wood and humus white-rot basidiomycetes) and three taxonomical groups (orders Polyporales, Hymenochaetales and Agaricales). Depending on the above groups, different decolorization zones were observed on the dye-containing plates, being restricted to the colony area or extending to the surrounding medium, which suggested two different decay strategies. These two strategies were related to the ability to secrete peroxidases and laccases inside (white-rot wood Polyporales, Hymenochaetales and Agaricales) and outside (white-rot humus Agaricales) of the fungal colony, as revealed by enzymatic tests performed directly on the agar plates. Similar oxidoreductases production patterns were observed when fungi were grown in the absence of dyes, although the set of enzyme released was different. All these results suggest that the decolorization patterns observed could be related with the existence of two decay strategies developed by white-rot basidiomycetes adapted to wood and leaf litter decay in the field. Published by Elsevier Inc.

Synthesis of low-cost adsorbent from rice bran for the removal of reactive dye based on the response surface methodology

NASA Astrophysics Data System (ADS)

Hong, Gui-Bing; Wang, Yi-Kai

2017-11-01

Rice bran is a major by-product of the rice milling industry and is abundant in Taiwan. This study proposed a simple method for modifying rice bran to make it a low-cost adsorbent to remove reactive blue 4 (RB4) from aqueous solutions. The effects of independent variables such as dye concentration (100-500 ppm), adsorbent dosage (20-120 mg) and temperature (30-60 °C) on the dye adsorption capacity of the modified rice bran adsorbent were investigated by using the response surface methodology (RSM). The results showed that the dye maximum adsorption capacity of the modified rice bran adsorbent was 151.3 mg g-1 with respect to a dye concentration of 500 ppm, adsorbent dosage of 65.36 mg, and temperature of 60 °C. The adsorption kinetics data followed the pseudo-second-order kinetic model, and the isotherm data fit the Langmuir isotherm model well. The maximum monolayer adsorption capacity was 178.57-185.19 mg g-1, which was comparable to that of other agricultural waste adsorbents used to remove RB4 from aqueous solutions in the literature. The thermodynamics analysis results indicated that the adsorption of RB4 onto the modified rice bran adsorbent is an endothermic, spontaneous monolayer adsorption that occurs through a physical process.

Degradation of immobilized azo dyes by Klebsiella sp. UAP-b5 isolated from maize bioadsorbent.

PubMed

Elizalde-González, M P; Fuentes-Ramírez, L E; Guevara-Villa, M R G

2009-01-30

The degradation of two immobilized dyes by Klebsiella sp. UAP-b5 was studied. In batch experiments, the azo dyestuffs Basic Blue 41 and Reactive Black 5 were immobilized onto corn cobs by adsorption, and the adsorption process was characterized by a pseudo-second-order kinetic equation. Klebsiella sp. UAP-b5 was previously isolated from the corn waste and shown to decolorize these dyes in liquid systems. Here, we demonstrate anaerobic decolorization and reductive biodegradation of these dyes by means of spectrophotometry, HPLC, and IR spectroscopy of the solid waste and desorption solutions. We also demonstrate adsorption of compounds that resemble known degradation products.

Tilted Orientation of Photochromic Dyes with Guest-Host Effect of Liquid Crystalline Polymer Matrix for Electrical UV Sensing

PubMed Central

Ranjkesh, Amid; Park, Min-Kyu; Park, Do Hyuk; Park, Ji-Sub; Choi, Jun-Chan; Kim, Sung-Hoon; Kim, Hak-Rin

2015-01-01

We propose a highly oriented photochromic dye film for an ultraviolet (UV)-sensing layer, where spirooxazine (SO) derivatives are aligned with the liquid crystalline UV-curable reactive mesogens (RM) using a guest-host effect. For effective electrical UV sensing with a simple metal-insulator-metal structure, our results show that the UV-induced switchable dipole moment amount of the SO derivatives is high; however, their tilting orientation should be controlled. Compared to the dielectric layer with the nearly planar SO dye orientation, the photochromic dielectric layer with the moderately tilted dye orientation shows more than seven times higher the UV-induced capacitance variation. PMID:26729116

High laser efficiency and photostability of pyrromethene dyes mediated by nonpolar solvent.

PubMed

Gupta, Monika; Kamble, Priyadarshini; Rath, M C; Naik, D B; Ray, Alok K

2015-08-10

Many pyrromethene (PM) dyes have been shown to outperform established rhodamine dyes in terms of laser efficiency in the green-yellow spectral region, but their rapid photochemical degradation in commonly used ethanol or methanol solvents continues to limit its use in high average power liquid dye lasers. A comparative study on narrowband laser efficiency and photostability of commercially available PM567 and PM597 dyes, using nonpolar n-heptane and 1,4-dioxane and polar ethanol solvents, was carried out by a constructed pulsed dye laser, pumped by the second harmonic (532 nm) radiation of a Q-switched Nd:YAG laser. Interestingly, both nonpolar solvents showed a significantly higher laser photostability (∼100 times) as well as peak efficiency (∼5%) of these PM dyes in comparison to ethanol. The different photostability of the PM dyes was rationalized by determining their triplet-state spectra and capability to generate reactive singlet oxygen (O₂1) by energy transfer to dissolved oxygen in these solvents using pulse radiolysis. Heptane is identified as a promising solvent for these PM dyes for use in high average power dye lasers, pumped by copper vapor lasers or diode-pumped solid-state green lasers.

Phase I study of 6-diazo-5-oxo-L-norleucine (DON).

PubMed

Sklaroff, R B; Casper, E S; Magill, G B; Young, C W

1980-01-01

We conducted a phase I study of 6-diazo-5-oxo-L-norleucine given iv on a twice weekly schedule. Twenty-six evaluable patients received 31 courses of the drug. Doses ranged from 100 to 500 mg/m2. Nausea with vomiting was the dose-limiting toxic effect, transient thrombocytopenia was seen frequently, and mucositis occurred in 39% of the patients. No definite therapeutic responses were observed in 18 patients with measurable lesions. The recommended dose for phase II studies is 200-300 mg/m2 iv twice weekly.

Trifluoromethylthiolation and Trifluoromethylselenolation of α-Diazo Esters Catalyzed by Copper.

PubMed

Matheis, Christian; Krause, Thilo; Bragoni, Valentina; Goossen, Lukas J

2016-08-22

α-Diazo esters are smoothly converted into the corresponding trifluoromethyl thio- or selenoethers by reaction with Me4 NSCF3 or Me4 NSeCF3 , respectively, in the presence of catalytic amounts of copper thiocyanate. This straightforward method gives high yields under neutral conditions at room temperature and is applicable to a wide range of functionalized molecules, including diverse α-amino acid derivatives. It is well-suited for the late-stage introduction of trifluoromethylthio or -seleno groups into drug-like molecules. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid and sensitive detection of clenbuterol using a fluorescence nanosensor based on diazo coupling mechanism

NASA Astrophysics Data System (ADS)

Thanh Hop Tran, Thi; Huong Do, Thi Mai; Hoang, Mai Ha; Tuyen Nguyen, Duc; Le, Quang Tuan; Nghia Nguyen, Duc; Ngo, Trinh Tung

2015-01-01

In this paper, the fluorescence resonance energy transfer (FRET) effect has been used for fabrication of nanosensor for the detection of clenbuterol. In the nanosensor, the CdTe quantum dots (QDs) are the donors while the acceptor is the super-macromolecule formed by the diazoation coupling mechanism between diazo clenbuterol and naphthylethylene diamine. Changes in fluorescence intensities of nanosensor were used to determine the clenbuterol concentration. We have successfully fabricated a nanosensor for detection of clenbuterol sensible to clenbuterol concentration of 10-12 g ml-1.

Textile wastewater treatment: colour and COD removal of reactive black-5 by ozonation

NASA Astrophysics Data System (ADS)

Suryawan, I. W. K.; Helmy, Q.; Notodarmojo, S.

2018-01-01

Textile industries produced a large amount of highly coloured wastewater containing variety of dyes in different concentrations. Due to the high concentration of organics in the effluents and the higher stability of modern synthetic dyes, the conventional biological treatment methods are ineffective for the complete colour removal and degradation of organics and dyes. On the other hand, physical-chemical treatment are not destructive, mainly just concentrate and separate the pollutants phases. This research paper investigates the removal of colour and chemical oxygen demand/COD from textile wastewater using ozone treatment. Varied ozone dosages of 1.16; 3.81; 18.79; and 40.88 mg/minute were used in the experiment. Varied wastewater containing Reactive Black 5 (RB-5) concentrations of 40 mg/L, 100 mg/L were also applied. Research result showed the highest colour removal efficiency of 96.9 % was achieved after 5 hours incubation time, while the highest COD removal efficiency of 77.5% was achieved after 2 hours incubation time.

Metabolite screening of aromatic amine hair dyes using in vitro hepatic models.

PubMed

Skare, J A; Hewitt, N J; Doyle, E; Powrie, R; Elcombe, C

2009-11-01

Aromatic amines and heterocyclic amines are widely used ingredients in permanent hair dyes. However, little has been published on their potential for oxidation via hepatic cytochrome P450s. Therefore, the authors screened nine such compounds for their potential to undergo oxidative metabolism in human liver microsomes. Toluene-2,5-diamine (TDA), p-aminophenol, m-aminophenol, p-methylaminophenol, N,N'-bis(2-hydroxyethyl)-p-phenylenediamine, and 1-hydroxyethyl-4,5-diaminopyrazole showed no evidence of oxidative metabolism. Oxidized metabolites of 4-amino-2-hydroxytoluene (AHT), 2-methyl-5- hydroxyethylaminophenol (MHEAP), and phenyl methyl pyrazolone (PMP) were detected, but there was no evidence of beta-nicotinamide adenine dinucleotide phosphate (NADPH)-dependent covalent binding to microsomal protein, suggesting that these are not reactive metabolites. Metabolism of AHT, MHEAP, PMP, and TDA was further studied in human hepatocytes. All these compounds underwent conjugation, but no oxidative metabolites were found. The results suggest that none of the hair dye ingredients tested showed evidence of hepatic metabolism to potentially biologically reactive oxidized metabolites.

Degradation and ecotoxicity of dye Reactive Black 5 after reductive-oxidative process : Environmental Science and Pollution Research.

PubMed

Cuervo Lumbaque, Elisabeth; Gomes, Monike Felipe; Da Silva Carvalho, Vanessa; de Freitas, Adriane Martins; Tiburtius, Elaine Regina Lopes

2017-03-01

This research paper describes the study of a reduction-oxidation system using commercial steel wool (Fe 0 ) and H 2 O 2 for degradation of the dye Reactive Black 5 and aromatic compounds in water. The reductive process alone allowed the almost complete removal of color (97 ± 1 %) after 60 min of reaction. The decrease in spectral area (λ = 599 nm) associated with the chromophore group indicates breakage of the azo bonds. Moreover, the significant change in UV spectra can be associated with the formation of aromatic amines. Regarding the transformation products, a spectrophotometric method based on the diazotization reaction was employed to identify aromatic amines after reductive process, using sulfanilic acid as a model of aromatic amines. In addition, association with Fenton reagents improved the efficiency in the system with 93 ± 1 % degradation of intermediates formed during the reductive process. Ecotoxicological analysis revealed that the dye solution, after the reductive and oxidative processes, was not toxic to Lactuca sativa seeds. For Daphnia magna, the EC 50 (%) values observed revealed that dye solution has an EC 50 (%) = 74.1 and after reductive process, the toxicity increased (EC 50 (%) = 63.5), which might be related to the formation of aromatic amines. However, after the Fenton process, the EC 50 (%) was >100. These results demonstrated that the Fenton reaction using steel wool as an iron source was very efficient to decrease color, aromatic transformation products, and the ecotoxicity of Reactive Black 5 in solution.

Optimization of degradation of Reactive Black 5 (RB5) and electricity generation in solar photocatalytic fuel cell system.

PubMed

Khalik, Wan Fadhilah; Ho, Li-Ngee; Ong, Soon-An; Voon, Chun-Hong; Wong, Yee-Shian; Yusoff, NikAthirah; Lee, Sin-Li; Yusuf, Sara Yasina

2017-10-01

The photocatalytic fuel cell (PFC) system was developed in order to study the effect of several operating parameters in degradation of Reactive Black 5 (RB5) and its electricity generation. Light irradiation, initial dye concentration, aeration, pH and cathode electrode are the operating parameters that might give contribution in the efficiency of PFC system. The degradation of RB5 depends on the presence of light irradiation and solar light gives better performance to degrade the azo dye. The azo dye with low initial concentration decolorizes faster compared to higher initial concentration and presence of aeration in PFC system would enhance its performance. Reactive Black 5 rapidly decreased at higher pH due to the higher amount of OH generated at higher pH and Pt-loaded carbon (Pt/C) was more suitable to be used as cathode in PFC system compared to Cu foil and Fe foil. The rapid decolorization of RB5 would increase their voltage output and in addition, it would also increase their V oc , J sc and P max . The breakage of azo bond and aromatic rings was confirmed through UV-Vis spectrum and COD analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Optimization and mechanisms for biodecoloration of a mixture of dyes by Trichosporon akiyoshidainum HP 2023.

PubMed

Martorell, María M; Rosales Soro, María Del M; Pajot, Hipólito F; de Figueroa, Lucía I C

2017-09-16

Trichosporon akiyoshidainum HP2023 is a basidiomycetous yeast isolated from Las Yungas rainforest (Tucumán, Argentina) and selected based on its outstanding textile-dye-decolorizing ability. In this work, the decolorization process was optimized using Reactive Black 5 as dye model. Lactose and urea were chosen as carbon and nitrogen sources through a one-at-time approach. Afterwards, factorial designs were employed for medium optimization, leading to the formulation of a simpler optimized medium which contains in g L -1 : lactose 10, yeast extract 1, urea 0.5, KH 2 PO 4 1 and MgSO 4 1. Temperature and agitation conditions were also optimized. The optimized medium and incubation conditions for dye removal were extrapolated to other dyes individually and a mixture of them. Dye removal process happened through both biosorption and biodegradation mechanisms, depending primarily on the dye structure. A positive relation between initial inoculum and dye removal rate and a negative relation between initial dye concentration and final dye removal percentages were found. Under optimized conditions, T. akiyoshidainum HP2023 was able to completely remove a mixture of dyes up to a concentration of 300 mg L -1 , a concentration much higher than those expected in real effluents.

Application of H2O and UV/H2O2 processes for enhancing the biodegradability of reactive black 5 dye.

PubMed

Kalpana, S Divya; Kalyanaraman, Chitra; Gandhi, N Nagendra

2011-07-01

Leather processing is a traditional activity in India during which many organic and inorganic chemicals are added while part of it is absorbed by the leather, the remaining chemicals are discharged along with the effluent. The effluent contains both easily biodegradable and not easily biodegradable synthetic organics like dyes, syntans. Easily biodegradable organics are removed in the existing biological treatment units whereas synthetic organics present in the wastewater are mostly adsorbed over the microbes. As the tannery effluent contains complex chemicals, it is difficult to ascertain the degradation of specific pollutants. To determine the increase in the biodegradability, one of the complex and synthetic organic chemical like dye used in the tanning operation was selected for Advanced Oxidation Process (AOPs) treatment for cleaving complex organics and its subsequent treatment in aerobic process. In the present study, Reactive Black 5 Dye used in the tanning operation was selected for Hydrogen Peroxide (H2O2) and UV/H2O2 pre-treatment for different operating conditions like pH, contact time and different volume of H2O2. A comparison was made between the untreated, Hydrogen Peroxide (H2O2) and UV/H2O2 treated effluent in order to ascertain the influence of AOP on the improvement of biodegradability of effluent. An increase in the BOD5/COD ratio from 0.21 to 0.435 was achieved in the UV/H2O2 pre-treatment process. This pre-treated effluent was further subjected to aerobic process. Biochemical Oxygen Demand (BOD5) and Chemical Oxygen Demand (COD) removal efficiency of the UV/H2O2 pre-treated dye solution in the aerobic process was found to be 86.39% and 77.82% when compared to 52.43% of BOD5 and 51.55% of COD removal efficiency without any pre-treatment. Hence from these results, to increase the biodegradability of Reactive Black 5 dye pre-treatment methods like H2O2 and UV/H2O2 can be used prior to biological treatment process.

Polar red-emitting rhodamine dyes with reactive groups: synthesis, photophysical properties, and two-color STED nanoscopy applications.

PubMed

Kolmakov, Kirill; Wurm, Christian A; Meineke, Dirk N H; Göttfert, Fabian; Boyarskiy, Vadim P; Belov, Vladimir N; Hell, Stefan W

2014-01-03

The synthesis, reactivity, and photophysical properties of new rhodamines with intense red fluorescence, two polar residues (hydroxyls, primary phosphates, or sulfonic acid groups), and improved hydrolytic stability of the amino-reactive sites (NHS esters or mixed N-succinimidyl carbonates) are reported. All fluorophores contain an N-alkyl-1,2-dihydro-2,2,4-trimethylquinoline fragment, and most of them bear a fully substituted tetrafluoro phenyl ring with a secondary carboxamide group. The absorption and emission maxima in water are in the range of 635-639 and 655-659 nm, respectively. A vastly simplified approach to red-emitting rhodamines with two phosphate groups that are compatible with diverse functional linkers was developed. As an example, a phosphorylated dye with an azide residue was prepared and was used in a click reaction with a strained alkyne bearing an N-hydroxysuccinimid (NHS) ester group. This method bypasses the undesired activation of phosphate groups, and gives an amphiphilic amino-reactive dye, the solubility and distribution of which between aqueous and organic phases can be controlled by varying the pH. The presence of two hydroxyl groups and a phenyl ring with two carboxyl residues in the dyes with another substitution pattern is sufficient for providing the hydrophilic properties. Selective formation of a mono-N-hydroxysuccinimidyl ester from 5-carboxy isomer of this rhodamine is reported. The fluorescence quantum yields varied from 58 to 92% for free fluorophores, and amounted to 18-64% for antibody conjugates in aqueous buffers. The brightness and photostability of these fluorophores facilitated two-color stimulated emission depletion (STED) fluorescence nanoscopy of biological samples with high contrast and minimal background. Selecting a pair of fluorophores with absorption/emission bands at 579/609 and 635/655 nm enabled two-color channels with low cross-talk and negligible background at approximately 40 nm resolution. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Clean Photothermal Heating and Controlled Release from Near-Infrared Dye Doped Nanoparticles without Oxygen Photosensitization.

PubMed

Guha, Samit; Shaw, Scott K; Spence, Graeme T; Roland, Felicia M; Smith, Bradley D

2015-07-21

The photothermal heating and release properties of biocompatible organic nanoparticles, doped with a near-infrared croconaine (Croc) dye, were compared with analogous nanoparticles doped with the common near-infrared dyes ICG and IR780. Separate formulations of lipid-polymer hybrid nanoparticles and liposomes, each containing Croc dye, absorbed strongly at 808 nm and generated clean laser-induced heating (no production of (1)O2 and no photobleaching of the dye). In contrast, laser-induced heating of nanoparticles containing ICG or IR780 produced reactive (1)O2, leading to bleaching of the dye and also decomposition of coencapsulated payload such as the drug doxorubicin. Croc dye was especially useful as a photothermal agent for laser-controlled release of chemically sensitive payload from nanoparticles. Solution state experiments demonstrated repetitive fractional release of water-soluble fluorescent dye from the interior of thermosensitive liposomes. Additional experiments used a focused laser beam to control leakage from immobilized liposomes with very high spatial and temporal precision. The results indicate that fractional photothermal leakage from nanoparticles doped with Croc dye is a promising method for a range of controlled release applications.

Clean Photothermal Heating and Controlled Release From Near Infrared Dye Doped Nanoparticles Without Oxygen Photosensitization

PubMed Central

Guha, Samit; Shaw, Scott K.; Spence, Graeme T.; Roland, Felicia M.; Smith, Bradley D.

2015-01-01

The photothermal heating and release properties of biocompatible organic nanoparticles, doped with a near-infrared croconaine (Croc) dye, were compared with analogous nanoparticles doped with the common near-infrared dyes ICG and IR780. Separate formulations of lipid-polymer-hybrid nanoparticles and liposomes, each containing Croc dye, absorbed strongly at 808 nm and generated clean laser-induced heating (no production of 1O2 and no photobleaching of the dye). In contrast, laser-induced heating of nanoparticles containing ICG or IR780 produced reactive 1O2 leading to bleaching of the dye and also decomposition of co-encapsulated payload such as the drug Doxorubicin. Croc dye was especially useful as a photothermal agent for laser controlled release of chemically sensitive payload from nanoparticles. Solution state experiments demonstrated repetitive fractional release of water soluble fluorescent dye from the interior of thermosensitive liposomes. Additional experiments used a focused laser beam to control leakage from immobilized liposomes with very high spatial and temporal precision. The results indicate that fractional photothermal leakage from nanoparticles doped with Croc dye is a promising method for a range of controlled release applications. PMID:26149326

On the structure of transition metals complexes with the new tridentate dye of thiazole series: Theoretical and experimental studies

NASA Astrophysics Data System (ADS)

Fizer, Maksym; Sidey, Vasyl; Tupys, Andrii; Ostapiuk, Yurii; Tymoshuk, Oleksandr; Bazel, Yaroslav

2017-12-01

The 1-[(5-Benzyl-1,3-thiazol-2-yl)diazenyl]naphthalene-2-ol (BnTAN) is a recently synthesized azo dye that can act as a tridentate ligand in complexes with transition metals. In a series of previous works, this analytical reagent was shown to be applicable for selective, reliable, express and relatively inexpensive determination of heavy metals in different objects through the spectrophotometric technique. Although the action of 1-(2-thiazolylazo)-2-naphthol (TAN) dyes as tridentate ligands has been suggested in the literature long time ago, due to the lack of experimental data, it was necessary to investigate the mechanism of formation and the structure of BnTAN complexes with the such transition metals as Cu(II), Zn(II) and Cd(II). Furthermore, the reactivity and properties of different acidity forms and conformers of BnTAN and related TAN dyes were not fully defined, so the determination of these properties by analysis of wavefunction was also necessary. Two standard spectrophotometric methods and voltammetric technique were used to determine the composition of complex of BnTAN with metals ions. All three experimental methods indicate that coordination ratio of metal:dye is equal to 1:2. Moreover, this study reports the stability and geometry of conformers of different forms (anionic/neutral/cationic) of BnTAN, along with a detailed analysis of electronic properties, reactivity and aromaticity of the most stable conformers of BnTAN forms. Each of the above forms has some difference in position of benzyl ring against the thiazole moiety, which is explained in terms of attraction and repulsion of these two fragments induced by partial atomic charges. The crucial influence of hydrogen bond and weak non-covalent interactions between naphthyl, aza- and thiazolyl fragments has been established. The quantum chemical calculations have shown that partial atomic charges of anionic, neutral and cationic forms can explain the reactivity of each BnTAN form, and have also clarified the mechanism of formation of metal complex through the connection of metal with phenol oxygen, thiazolyl nitrogen and one nitrogen of aza group - thus giving two five-membered metal-containing cycles and confirming that BnTAN acts as a tridentate ligand. The obtained results introduce novel and crucial information which can assist in understanding the mechanism of complex formation of BnTAN and display the strength and level of detail of applying quantum chemical methods to reveal the reactivity, energy properties, and electronic properties of this new dye.

Noncovalent labeling of biomolecules with red and near- infrared dyes.

PubMed

Patonay, Gabor; Salon, Jozef; Sowell, John; Strekowski, Lucjan

2004-02-28

Biopolymers such as proteins and nucleic acids can be labeled with a fluorescent marker to allow for their detection. Covalent labeling is achieved by the reaction of an appropriately functionalized dye marker with a reactive group on a biomolecule. The recent trend, however, is the use of noncovalent labeling that results from strong hydrophobic and/or ionic interactions between the marker and biomolecule of interest. The main advantage of noncovalent labeling is that it affects the functional activity of the biomolecule to a lesser extent. The applications of luminescent cyanine and squarylium dyes are reviewed.

1,7-Cyclization of 1-diazo-2,4-pentadiene and its heteroanalogues: DFT study

NASA Astrophysics Data System (ADS)

Subbotina, Julia O.; Bakulev, V. A.; Herges, R.; Fabian, W. M. F.

1,7-Dipolar cyclizations of 1-diazo-2,4-pentadiene 1a and its heteroanalogues 1b,c and 4c were studied using density functional theory (DFT). Although the heteroanalogue 1c has an appropriate electronic structure to allow for pseudopericyclic cyclization, natural bond order (NBO) analysis has provided evidence for the electrocyclic ring closure. Magnetic criteria (anisotropy of the induced current density [ACID], nucleus-independent chemical shifts [NICS]) confirmed the pericyclic character of the located transition states 2a,c and 5c. The activation barriers for the cyclization of 1-diazo-2,4-pentadiene 1a and its aza analogues 1c, 4c are 3.3, 8.2, and 12.3 kcal/mol at the B3LYP/6-31G(d) level, respectively. The higher barrier of the 1c?3c and 4c?3c reactions compared with 1a?3a is in line with the Hammond postulate. The out-of-plane distorted geometry of the cyclic product is an additional factor arguing against a pseudopericyclic mechanism.

Reviving Lonidamine and 6-Diazo-5-oxo-L-norleucine to Be Used in Combination for Metabolic Cancer Therapy

PubMed Central

Cervantes-Madrid, Diana; Romero, Yair; Dueñas-González, Alfonso

2015-01-01

Abnormal metabolism is another cancer hallmark. The two most characterized altered metabolic pathways are high rates of glycolysis and glutaminolysis, which are natural targets for cancer therapy. Currently, a number of newer compounds to block glycolysis and glutaminolysis are being developed; nevertheless, lonidamine and 6-diazo-5-oxo-L-norleucine (DON) are two old drugs well characterized as inhibitors of glycolysis and glutaminolysis, respectively, whose clinical development was abandoned years ago when the importance of cancer metabolism was not fully appreciated and clinical trial methodology was less developed. In this review, a PubMed search using the words lonidamine and 6-diazo-5-oxo-L-norleucine (DON) was undertaken to analyse existing information on the preclinical and clinical studies of these drugs for cancer treatment. Data show that they exhibit antitumor effects; besides there is also the suggestion that they are synergistic. We conclude that lonidamine and DON are safe and potentially effective drugs that need to be reevaluated in combination as metabolic therapy of cancer. PMID:26425550

Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse Reaction of α-Diazo Pyrazoleamides.

PubMed

Lin, Xiaobin; Tang, Yu; Yang, Wei; Tan, Fei; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming

2018-03-07

Although high enantioselectivity of [2,3]-sigmatropic rearrangement of sulfonium ylides (Doyle-Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty in fine discrimination of the heterotopic lone pairs of sulfur and chirality inversion at sulfur of sulfonium ylides. Here, we show that the synergistic merger of new α-diazo pyrazoleamides and a chiral N, N'-dioxide-nickel(II) complex catalyst enables a highly enantioselective Doyle-Kirmse reaction. The pyrazoleamide substituent serves as both an activating and a directing group for the ready formation of a metal-carbene- and Lewis-acid-bonded ylide intermediate in the assistance of a dual-tasking nickel(II) complex. An alternative chiral Lewis-acid-bonded ylide pathway greatly improves the product enantiopurity even for the reaction of a symmetric diallylsulfane. The majority of transformations over a series of aryl- or vinyl-substituted α-diazo pyrazoleamindes and sulfides proceed rapidly (within 5-20 min in most cases) with excellent results (up to 99% yield and 96% ee), providing a breakthrough in enantioselective Doyle-Kirmse reaction.

The Comparative Study on the Rapid Decolorization of Azo, Anthraquinone and Triphenylmethane Dyes by Anaerobic Sludge

PubMed Central

Cui, Daizong; Zhang, Hao; He, Rubao; Zhao, Min

2016-01-01

An anaerobic sludge (AS), capable of decolorizing a variety of synthetic dyes, was acclimated and is reported here. The sludge presented a much better dye decolorizing ability than that of different individual strains. A broad spectrum of dyes could be decolorized by the sludge. Continuous decolorization tests showed that the sludge exhibited the ability to decolorize repeated additions of dye. The chemical oxygen demand (COD) removal rate of the dye wastewater reached 52% after 12 h of incubation. Polymerase chain reaction and denaturing gradient gel electrophoresis (PCR-DGGE) profiles revealed that the microbial community changed as a result of varying initial concentrations of dyes. Phylogenetic analysis indicated that microbial populations in the sludge belonged to the phyla Acidobacteria, Firmicutes, Bacteroidetes, Chloroflexi and Proteobacteria. The degradation products of the three types of dye were identified. For azo dyes, the anaerobic sludge converted Methyl Orange to N,N-dimethylbenzene-1,4-diamine and 4-aminobenzenesulfonic acid; for triphenylmethane dyes, after Malachite Green was decolorized, the analyzed products were found to be a mixture of N,N-dimethylbenzenamine, 3-dimethyl-aminophenol and 4-dimethylaminobenzophenone; for anthraquinone dyes, two products (acetophenone and 2-methylbenzoic acid) were observed after Reactive Blue 19 decolorization. Together, these results suggest that the anaerobic sludge has promising potential for use in the treatment of industrial wastewater containing various types of dyes. PMID:27801853

Photodecomposition of dyes on Fe-C-TiO(2) photocatalysts under UV radiation supported by photo-Fenton process.

PubMed

Tryba, B; Piszcz, M; Grzmil, B; Pattek-Janczyk, A; Morawski, A W

2009-02-15

Fe-C-TiO(2) photocatalysts were prepared by mechanical mixing of commercial anatase TiO(2) precursor with FeC(2)O(4) and heating at 500-800 degrees C under argon flow. These photocatalysts were tested for dyes decomposition: Methylene Blue (MB), Reactive Black (RB) and Acid Red (AR). The preliminary adsorption of dyes on the photocatalysts surface was performed. Modification of anatase by FeC(2)O(4) caused reducing of zeta potential of the photocatalyst surface from +12 to -7mV and decreasing of their adsorption ability towards RB and AR, which were negatively charged, -46.8 and -39.7, respectively. Therefore, unmodified TiO(2) showed the highest degree of RB and AR decompositions in the combination of dyes adsorption and UV irradiation. Methylene Blue, which had zeta potential of +4.3 in the aqueous solution was poorly adsorbed on all the tested photocatalysts and also slowly decomposed under UV irradiation. The high rate of dyes decomposition was noted on Fe-C-TiO(2) photocatalysts under UV irradiation with addition of H(2)O(2). It was observed, that at lower temperatures of heat treatment such as 500 degrees C higher content of carbon is remained in the sample, blocking the built in of iron into the TiO(2) lattice. This iron is reactive in the photo-Fenton process resulting in high production of OH radicals and also high activity of the photocatalyst. At higher temperatures of heat treatment, less active FeTiO(3) phase is formed, therefore Fe-C-TiO(2) sample prepared at 800 degrees C showed low photocatalytic activity for dyes decomposition. Fe-C-TiO(2) photocatalysts are active under visible light irradiation, however, the efficiency of a dye decomposition is lower than under UV light. In a dark Fenton process there is observed an insignificant generation of OH radicals and very little decomposition of a dye, what suggests the powerful of photo-Fenton process in the dyes decomposition.

Biodegradation and detoxification of textile azo dyes by bacterial consortium under sequential microaerophilic/aerobic processes

PubMed Central

Lade, Harshad; Kadam, Avinash; Paul, Diby; Govindwar, Sanjay

2015-01-01

Release of textile azo dyes to the environment is an issue of health concern while the use of microorganisms has proved to be the best option for remediation. Thus, in the present study, a bacterial consortium consisting of Providencia rettgeri strain HSL1 and Pseudomonas sp. SUK1 has been investigated for degradation and detoxification of structurally different azo dyes. The consortium showed 98-99 % decolorization of all the selected azo dyes viz. Reactive Black 5 (RB 5), Reactive Orange 16 (RO 16), Disperse Red 78 (DR 78) and Direct Red 81 (DR 81) within 12 to 30 h at 100 mg L-1 concentration at 30 ± 0.2 °C under microaerophilic, sequential aerobic/microaerophilic and microaerophilic/aerobic processes. However, decolorization under microaerophilic conditions viz. RB 5 (0.26 mM), RO 16 (0.18 mM), DR 78 (0.20 mM) and DR 81 (0.23 mM) and sequential aerobic/microaerophilic processes viz. RB 5 (0.08 mM), RO 16 (0.06 mM), DR 78 (0.07 mM) and DR 81 (0.09 mM) resulted into the formation of aromatic amines. In distinction, sequential microaerophilic/ aerobic process doesn’t show the formation of amines. Additionally, 62-72 % reduction in total organic carbon content was observed in all the dyes decolorized broths under sequential microaerophilic/aerobic processes suggesting the efficacy of method in mineralization of dyes. Notable induction within the levels of azoreductase and NADH-DCIP reductase (97 and 229 % for RB 5, 55 and 160 % for RO 16, 63 and 196 % for DR 78, 108 and 258 % for DR 81) observed under sequential microaerophilic/aerobic processes suggested their critical involvements in the initial breakdown of azo bonds, whereas, a slight increase in the levels of laccase and veratryl alcohol oxidase confirmed subsequent oxidation of formed amines. Also, the acute toxicity assay with Daphnia magna revealed the nontoxic nature of the dye-degraded metabolites under sequential microaerophilic/aerobic processes. As biodegradation under sequential microaerophilic/aerobic process completely detoxified all the selected textile azo dyes, further efforts should be made to implement such methods for large scale dye wastewater treatment technologies. PMID:26417357

Ultrafiltration technology with a ceramic membrane for reactive dye removal: optimization of membrane performance.

PubMed

Alventosa-deLara, E; Barredo-Damas, S; Alcaina-Miranda, M I; Iborra-Clar, M I

2012-03-30

An ultrafiltration (UF) ceramic membrane was used to decolorize Reactive Black 5 (RB5) solutions at different dye concentrations (50 and 500 mg/L). Transmembrane pressure (TMP) and cross-flow velocity (CFV) were modified to study their influence on initial and steady-state permeate flux (J(p)) and dye rejection (R). Generally, J(p) increased with higher TMP and CFV and lower feed concentration, up to a maximum steady-state J(p) of 266.81 L/(m(2)h), obtained at 3 bar, 3m/s and 50mg/L. However, there was a TMP value (which changed depending on operating CFV and concentration) beyond which slight or no further increase in steady-state J(p) was observed. Similarly, the higher the CFV was, the more slightly the steady-state J(p) increased. Furthermore, the effectiveness of ultrafiltration treatment was evaluated through dye rejection coefficient. The results showed significant dye removals, regardless of the tested conditions, with steady-state R higher than 79.8% for the 50mg/L runs and around 73.2% for the 500 mg/L runs. Finally response surface methodology (RSM) was used to optimize membrane performance. At 50mg/L, a TMP of 4 bar and a CFV of 2.53 m/s were found to be the conditions giving the highest steady-state J(p), 255.86 L/(m(2)h), and the highest R, 95.2% simultaneously. Copyright © 2012 Elsevier B.V. All rights reserved.

Rh-Catalyzed Intermolecular Reactions of α-Alkyl-α-Diazo Carbonyl Compounds with Selectivity over β-Hydride Migration.

PubMed

DeAngelis, Andrew; Panish, Robert; Fox, Joseph M

2016-01-19

Rh-carbenes derived from α-diazocarbonyl compounds have found broad utility across a remarkable range of reactivity, including cyclopropanation, cyclopropenation, C-H insertions, heteroatom-hydrogen insertions, and ylide forming reactions. However, in contrast to α-aryl or α-vinyl-α-diazocarbonyl compounds, the utility of α-alkyl-α-diazocarbonyl compounds had been moderated by the propensity of such compounds to undergo intramolecular β-hydride migration to give alkene products. Especially challenging had been intermolecular reactions involving α-alkyl-α-diazocarbonyl compounds. This Account discusses the historical context and prior limitations of Rh-catalyzed reactions involving α-alkyl-α-diazocarbonyl compounds. Early studies demonstrated that ligand and temperature effects could influence chemoselectivity over β-hydride migration. However, effects were modest and conflicting conclusions had been drawn about the influence of sterically demanding ligands on β-hydride migration. More recent advances have led to a more detailed understanding of the reaction conditions that can promote intermolecular reactivity in preference to β-hydride migration. In particular, the use of bulky carboxylate ligands and low reaction temperatures have been key to enabling intermolecular cyclopropenation, cyclopropanation, carbonyl ylide formation/dipolar cycloaddition, indole C-H functionalization, and intramolecular bicyclobutanation with high chemoselectivity over β-hydride migration. Cyclic α-diazocarbonyl compounds have been shown to be particularly resilient toward β-hydride migration and are the first class of compounds that can engage in intermolecular reactivity in the presence of tertiary β-hydrogens. DFT calculations were used to propose that for cyclic α-diazocarbonyl compounds, ring constraints relieve steric interaction for intermolecular reactions and thereby accelerate the rate of intermolecular reactivity relative to intramolecular β-hydride migration. Enantioselective reactions of α-alkyl-α-diazocarbonyl compounds have been developed using bimetallic N-imido-tert-leucinate-derived complexes. The most effective complexes were found by computation and X-ray crystallography to adopt a "chiral crown" conformation in which all of the imido groups are presented on one face of the paddlewheel complex in a chiral arrangement. Insight from computational studies guided the design and synthesis of a mixed ligand paddlewheel complex, Rh2(S-PTTL)3TPA, the structure of which bears similarity to the chiral crown complex Rh2(S-PTTL)4. Rh2(S-PTTL)3TPA engages substrate classes (aliphatic alkynes, silylacetylenes, α-olefins) that are especially challenging in intermolecular reactions of α-alkyl-α-diazoesters and catalyzes enantioselective cyclopropanation, cyclopropenation, and indole C-H functionalization with yields and enantioselectivities that are comparable or superior to Rh2(S-PTTL)4. The work detailed in this Account describes progress toward enabling a more general utility for α-alkyl-α-diazo compounds in Rh-catalyzed carbene reactions. Further studies on ligand design and synthesis will continue to broaden the scope of their selective reactions.

Stereodivergent Synthesis of N-Heterocycles by Catalyst-Controlled, Activity-Directed Tandem Annulation of Diazo Compounds with Amino Alkynes.

PubMed

Liu, Kai; Zhu, Chenghao; Min, Junxiang; Peng, Shiyong; Xu, Guangyang; Sun, Jiangtao

2015-10-26

A stereodivergent synthesis of five-membered N-heterocycles, such as 2,3-dihydropyrroles, and 2-methylene and 3-methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper-catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium-catalyzed protocol features a carbenoid insertion into the NH bond and subsequent Conia-ene cyclization. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochemical transformations of diazocarbonyl compounds: expected and novel reactions

NASA Astrophysics Data System (ADS)

Galkina, O. S.; Rodina, L. L.

2016-05-01

Photochemical reactions of diazocarbonyl compounds are well positioned in synthetic practice as an efficient method for ring contraction and homologation of carboxylic acids and as a carbene generation method. However, interpretation of the observed transformations of diazo compounds in electronically excited states is incomplete and requires a careful study of the fine mechanisms of these processes specific to different excited states of diazo compounds resorting to modern methods of investigation, including laser technology. The review is devoted to analysis of new data in the chemistry of excited states of diazocarbonyl compounds. The bibliography includes 155 references.

Photoactive layer based on T-shaped benzimidazole dyes used for solar cell: from photoelectric properties to molecular design

NASA Astrophysics Data System (ADS)

Xu, Beibei; Li, Yuanzuo; Song, Peng; Ma, Fengcai; Sun, Mengtao

2017-03-01

Three benzimidazole-based organic dyes, possessing the same triphenylamine donors and cyanoacrylic acid acceptors with the bithiophene π-bridges combined in different nuclear positions of benzimidazole, were investigated in the utility of dye-sensitizer solar cells. The structure, molecular orbital and energy, absorption spectra and some important parameters (such as light harvesting efficiency (LHE), electron injection driving force, the electron injection time, chemical reactivity parameters, vertical dipole moment as well as interaction models of dye-I2) were obtained according to Newns-Anderson model and DFT calculation. The process and strength of charge transfer and separation were visualized with charge different density and index of spatial extent (S, D and Δq). Current work paid attention to the new T-shaped dyes to reveal the relation between the structure and photoelectric performance. Furthermore, nine dyes (substitution of alkyl chains and π-bridges) have been designed and characterized to screen promising sensitizer candidates with excellent photo-electronic properties.

Cellulose nanocrystal-reinforced keratin bioadsorbent for effective removal of dyes from aqueous solution.

PubMed

Song, Kaili; Xu, Helan; Xu, Lan; Xie, Kongliang; Yang, Yiqi

2017-05-01

High-efficiency and recyclable three-dimensional bioadsorbents were prepared by incorporating cellulose nanocrystal (CNC) as reinforcements in keratin sponge matrix to remove dyes from aqueous solution. Adsorption performance of dyes by CNC-reinforced keratin bioadsorbent was improved significantly as a result of adding CNC as filler. Batch adsorption results showed that the adsorption capacities for Reactive Black 5 and Direct Red 80 by the bioadsorbent were 1201 and 1070mgg -1 , respectively. The isotherms and kinetics for adsorption of both dyes on bioadsorbent followed the Langmuir isotherm model and pseudo-second order model, respectively. Desorption and regeneration experiments showed that the removal efficiencies of the bioadsorbent for both dyes could remain above 80% at the fifth recycling cycles. Moreover, the bioadsorbent possessed excellent packed-bed column operation performance. Those results suggested that the adsorbent could be considered as a high-performance and promising candidate for dye wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Parameters affecting the photocatalytic degradation of dyes using TiO2: a review

NASA Astrophysics Data System (ADS)

Reza, Khan Mamun; Kurny, ASW; Gulshan, Fahmida

2017-07-01

Traditional chemical, physical and biological processes for treating wastewater containing textile dye have such disadvantages as high cost, high energy requirement and generation of secondary pollution during treatment process. The advanced oxidation processes technology has been attracting growing attention for the decomposition of organic dyes. Such processes are based on the light-enhanced generation of highly reactive hydroxyl radicals, which oxidize the organic matter in solution and convert it completely into water, CO2 and inorganic compounds. In this presentation, the photocatalytic degradation of dyes in aqueous solution using TiO2 as photocatalyst under solar and UV irradiation has been reviewed. It is observed that the degradation of dyes depends on several parameters such as pH, catalyst concentration, substrate concentration and the presence of oxidants. Reaction temperature and the intensity of light also affect the degradation of dyes. Particle size, BET-surface area and different mineral forms of TiO2 also have influence on the degradation rate.

Dye removal from textile industrial effluents by adsorption on exfoliated graphite nanoplatelets: kinetic and equilibrium studies.

PubMed

Carvallho, Marilda N; da Silva, Karolyne S; Sales, Deivson C S; Freire, Eleonora M P L; Sobrinho, Maurício A M; Ghislandi, Marcos G

2016-01-01

The concept of physical adsorption was applied for the removal of direct and reactive blue textile dyes from industrial effluents. Commercial graphite nanoplatelets were used as substrate, and the quality of the material was characterized by atomic force and transmission electron microscopies. Dye/graphite nanoplatelets water solutions were prepared varying their pH and initial dye concentration. Exceptionally high values (beyond 100 mg/L) for adsorptive capacity of graphite nanoplatelets could be achieved without complicated chemical modifications, and equilibrium and kinetic experiments were performed. Our findings were compared with the state of the art, and compared with theoretical models. Agreement between them was satisfactory, and allowed us to propose novel considerations describing the interactions of the dyes and the graphene planar structure. The work highlights the important role of these interactions, which can govern the mobility of the dye molecules and the amount of layers that can be stacked on the graphite nanoplatelets surface.

Influence of azo dye concentration on activated sludge bacterial community in the presence of functionalized polyurethane foam.

PubMed

Lu, Hong; Wang, Jing; Lu, Shuilong; Wang, Ying; Liu, Guangfei; Zhou, Jiti; Quan, Zhexue

2015-03-01

Immobilized quinones exhibit good catalytic performance in the biodecolorization of azo dyes. However, in practical activated sludge systems, little is known about the effect of azo dye concentration on microbial communities in the presence of immobilized quinones. 454 Pyrosequencing was used to investigate structural changes and to determine the key microorganisms involved in Reactive Red X-3B decolorization in the presence of anthraquinone-2-sulfonate immobilized on polyurethane foam (AQS-PUF). Our results show that the AQS-PUF-supplemented system exhibited better stability and decolorization performance during a 30-day run than polyurethane-foam-only (PUF-supplemented) and control systems. Analysis of pyrosequencing data showed that the AQS-PUF-supplemented system had the highest bacterial diversity, followed by the control and PUF-supplemented systems during decolorization. Reactive Red X-3B and AQS-PUF significantly influenced bacterial communities at the class level: Erysipelotrichia and the most dominant Deltaproteobacteria showed significant positive correlations with Reactive Red X-3B, while unclassified Firmicutes were found to be significantly correlated with AQS-PUF. At the genus level, Desulfomicrobium, which represents 8-44 % of the total population, displayed a significant positive correlation with Reactive Red X-3B. Some bacteria, including Desulfovibrio, Shewanella, and Clostridium with relative abundances of less than 6 %, were positively correlated with AQS-PUF. These findings provide a novel insight into the changes that occur in the bacterial community during immobilized AQS-mediated decolorization. Less abundant quinone-reducing bacteria play important roles in accelerating the effect of AQS-PUF on biodecolorization.

Near-infrared dyes and upconverting phosphors as biomolecule labels and probes

NASA Astrophysics Data System (ADS)

Patonay, Gabor; Strekowski, Lucjan; Nguyen, Diem-Ngoc; Seok, Kim Jun

2007-02-01

Near-Infrared (NIR) absorbing chromophores have been used in analytical and bioanalytical chemistry extensively, including for determination of properties of biomolecules, DNA sequencing, immunoassays, capillary electrophoresis (CE) separations, etc. The major analytical advantages of these dyes are low background interference and high molar absorptivities. NIR dyes have additional advantages due to their sensitivity to microenvironmental changes. Spectral changes induced by the microenvironment are not desirable if the labels are used as a simple reporting group, e.g., during a biorecognition reaction. For these applications upconverting phosphors seem to be a better choice. There are several difficulties in utilizing upconverting phosphors as reporting labels. These are: large physical size, no reactive groups and insolubility in aqueous systems. This presentation will discuss how these difficulties can be overcome for bioanalytical and forensic applications. During these studies we also have investigated how to reduce physical size of the phosphor by simple grinding without losing activity and how to attach reactive moiety to the phosphor to covalently bind to the biomolecule of interest. It has to be emphasized that the described approach is not suitable for medical applications and the results of this research are not applicable in medical applications. For bioanalytical and forensic applications upconverting phosphors used as reporting labels have several advantages. They are excited with lasers that are red shifted respective to phosphorescence, resulting in no light scatter issues during detection. Also some phosphors are excited using eye safe lasers. In addition energy transfer to NIR dyes is possible, allowing detection schemes using donor-acceptor pairs. Data is presented to illustrate the feasibility of this phenomenon. If microenvironmental sensitivity is required, then specially designed NIR dyes can be used as acceptor labels. Several novel dyes have been synthesized in our laboratories for that purpose.

Synthesis of mesoporous TiO2-curcumin nanoparticles for photocatalytic degradation of methylene blue dye.

PubMed

Abou-Gamra, Z M; Ahmed, M A

2016-07-01

Herein, we demonstrate a facile route for synthesis a new photocatalyst based on TiO2-curcumin nanoparticles for photodegradation of methylene blue dye under UV and visible light irradiation. The photocatalyst was prepared by sol-gel method using chitosan as biodegradable polymer. The crystalline and the nanostructure were characteristic X-ray diffraction [XRD], adsorption-desorption isotherm and high resolution transmission electron microscopy [HRTEM]. However, the optical features of the samples were investigated by a UV-visible spectrophotometer. It is obvious to notice the removal of the majority of methylene blue dye on a pure titania surface via adsorption mechanism owing to the high surface area and to the organized mesoporous nature of the solid sample. Incorporation of curcumin on titania surface changes the removal direction from adsorption to the photocatalytic pathway. Various photocatalytic experiments were performed to investigate the influence of initial dye concentration, weight of catalyst, stirring and light intensity on the photocatalytic degradation of methylene blue as primary pollutant model. Chemical oxygen demand [COD] test confirms the complete degradation of methylene blue dye. The exceptional photocatalytic reactivity of titania-curcumin nanoparticles is referred to reduction in band gap energy and to the facility of electron transfer from II* curcumin energy level to titania conduction band which increases the concentration of reactive oxygen superoxide radicals which in turn prevents the electron-hole recombination. The effect of various scavengers on the methylene blue dye degradation was investigated using ethanol, ascorbic acid and methyl viologen. The results have pointed out that O2(-) and HO(.) are considered the main active species in the degradation process. A plausible pathway and mechanism for the photocatalytic degradation of methylene blue by titania-curcumin nanoparticles were illustrated. Copyright © 2016 Elsevier B.V. All rights reserved.

Significance of hair-dye base-induced sensory irritation.

PubMed

Fujita, F; Azuma, T; Tajiri, M; Okamoto, H; Sano, M; Tominaga, M

2010-06-01

Oxidation hair-dyes, which are the principal hair-dyes, sometimes induce painful sensory irritation of the scalp caused by the combination of highly reactive substances, such as hydrogen peroxide and alkali agents. Although many cases of severe facial and scalp dermatitis have been reported following the use of hair-dyes, sensory irritation caused by contact of the hair-dye with the skin has not been reported clearly. In this study, we used a self-assessment questionnaire to measure the sensory irritation in various regions of the body caused by two model hair-dye bases that contained different amounts of alkali agents without dyes. Moreover, the occipital region was found as an alternative region of the scalp to test for sensory irritation of the hair-dye bases. We used this region to evaluate the relationship of sensitivity with skin properties, such as trans-epidermal water loss (TEWL), stratum corneum water content, sebum amount, surface temperature, current perception threshold (CPT), catalase activities in tape-stripped skin and sensory irritation score with the model hair-dye bases. The hair-dye sensitive group showed higher TEWL, a lower sebum amount, a lower surface temperature and higher catalase activity than the insensitive group, and was similar to that of damaged skin. These results suggest that sensory irritation caused by hair-dye could occur easily on the damaged dry scalp, as that caused by skin cosmetics reported previously.

Spectroscopic investigation and direct comparison of the reactivities of iron pyridyl oxidation catalysts

NASA Astrophysics Data System (ADS)

Song, Yang; Mayes, Howard G.; Queensen, Matthew J.; Bauer, Eike B.; Dupureur, Cynthia M.

2017-03-01

The growing interest in green chemistry has fueled attention to the development and characterization of effective iron complex oxidation catalysts. A number of iron complexes are known to catalyze the oxidation of organic substrates utilizing peroxides as the oxidant. Their development is complicated by a lack of direct comparison of the reactivities of the iron complexes. To begin to correlate reactivity with structural elements, we compare the reactivities of a series of iron pyridyl complexes toward a single dye substrate, malachite green (MG), for which colorless oxidation products are established. Complexes with tetradentate, nitrogen-based ligands with cis open coordination sites were found to be the most reactive. While some complexes reflect sensitivity to different peroxides, others are similarly reactive with either H2O2 or tBuOOH, which suggests some mechanistic distinctions. [Fe(S,S-PDP)(CH3CN)2](SbF6)2 and [Fe(OTf)2(tpa)] transition under the oxidative reaction conditions to a single intermediate at a rate that exceeds dye degradation (PDP = bis(pyridin-2-ylmethyl) bipyrrolidine; tpa = tris(2-pyridylmethyl)amine). For the less reactive [Fe(OTf)2(dpa)] (dpa = dipicolylamine), this reaction occurs on a timescale similar to that of MG oxidation. Thus, the spectroscopic method presented herein provides information about the efficiency and mechanism of iron catalyzed oxidation reactions as well as about potential oxidative catalyst decomposition and chemical changes of the catalyst before or during the oxidation reaction.

A mitochondria-targeted turn-on fluorescent probe for the detection of glutathione in living cells.

PubMed

Zhang, Jian; Bao, Xiaolong; Zhou, Junliang; Peng, Fangfang; Ren, Hang; Dong, Xiaochun; Zhao, Weili

2016-11-15

A novel turn-on red fluorescent BODIPY-based probe (Probe 1) for the detection of glutathione was developed. Such a probe carries a para-dinitrophenoxy benzyl pyridinium moiety at the meso position of a BODIPY dye as self-immolative linker. Probe 1 responds selectively to glutathione with the detection limit of 109nM over other amino acids, common metal ions, reactive oxygen species, reactive nitrogen species, and reactive sulfur species. A novel electrostatic interaction to modulate the SNAr attack of glutathione was believed to play significant role for the observed selective response to glutathione. The cleavage of dinitrophenyl ether by glutathione leads to the production of para-hydroxybenzyl moiety which is able to self-immolate through an intramolecular 1,4-elimination reaction to release the fluorescent BODIPY dye. The low toxic probe has been successfully used to detect mitochondrial glutathione in living cells. Copyright © 2016 Elsevier B.V. All rights reserved.

Determinants of relaxation rate in rabbit skinned skeletal muscle fibres

PubMed Central

Luo, Ye; Davis, Jonathan P; Smillie, Lawrence B; Rall, Jack A

2002-01-01

The influence of Ca2+-activated force, the rate of dissociation of Ca2+ from troponin C (TnC) and decreased crossbridge detachment rate on the time course of relaxation induced by flash photolysis of diazo-2 in rabbit skinned psoas fibres was investigated at 15 °C. The rate of relaxation increased as the diazo-2 chelating capacity (i.e. free [diazo-2]/free [Ca2+]) increased. At a constant diazo-2 chelating capacity, the rate of relaxation was independent of the pre-photolysis Ca2+-activated force in the range 0.3-0.8 of maximum isometric force. A TnC mutant that exhibited increased Ca2+ sensitivity caused by a decreased Ca2+ dissociation rate in solution (M82Q TnC) also increased the Ca2+ sensitivity of steady-state force and decreased the rate of relaxation in fibres by approximately twofold. In contrast, a TnC mutant with decreased Ca2+ sensitivity caused by an increased Ca2+ dissociation rate in solution (NHdel TnC) decreased the Ca2+ sensitivity of steady-state force but did not accelerate relaxation. Decreasing the rate of crossbridge kinetics by reducing intracellular inorganic phosphate concentration ([Pi]) slowed relaxation by approximately twofold and led to two phases of relaxation, a slow linear phase followed by a fast exponential phase. In fibres, M82Q TnC further slowed relaxation in low [Pi] conditions by approximately twofold, whereas NHdel TnC had no significant effect on relaxation. These results are consistent with the interpretation that the Ca2+-dissociation rate and crossbridge detachment rate are similar in fast-twitch skeletal muscle, such that decreasing either rate slows relaxation, but accelerating Ca2+ dissociation has little effect on relaxation. PMID:12482894

Tailor-made biocatalysts based on scarcely studied acidic horseradish peroxidase for biodegradation of reactive dyes.

PubMed

Janović, Barbara S; Mićić Vićovac, Milica Lj; Vujčić, Zoran M; Vujčić, Miroslava T

2017-02-01

Peroxidases (EC 1.11.1.7) have enormous biotechnological applications. Usage of more abundant, basic isoforms of peroxidases in diagnostic kits and/or in immunochemistry has led to under exploitation and disregard of horseradish peroxidase (HRP) acidic isoforms. Therefore, acidic horseradish peroxidase (HRP-A) isoenzyme was used for the preparation of a biocatalyst with improved ability in dye decolorization. Ten biocatalysts were prepared by covalent binding of enzyme to chitosan and alginate, adsorption followed by cross-linking on inorganic support (aluminum oxide), and encapsulation in spherical calcium alginate beads via polyethylene glycol. Model dyes of 50 to 175 mg l -1 were removed by the biocatalysts. Among the tested biocatalysts, the three with the highest specific activity and biodegradation rate were further studied (Chitosan-HRP, Al-Gel-HRP and Al-HRP-Gel). The impact of hydrogen peroxide concentration on dye decolorization was examined on the Chitosan-HRP biocatalyst, since the HRP is susceptible to inhibition/inactivation by high H 2 O 2 . On the other hand, H 2 O 2 is needed as a co-substrate for the HRP, and the H 2 O 2 /dye ratio can greatly influence decolorization efficiency. Concentrations of H 2 O 2 ranging from 0.22 to 4.4 mM showed no difference in terms of impact on the biocatalyst decolorization efficiency. The high decolorization efficiency of the biocatalysts was validated by the removal of 25 and 100 mg l -1 anthraquinone (Remazol Brilliant Blue R (RBBR)), triphenylmethane (Coomassie Brilliant Blue (CBB)), acridine (Acridine Orange (AO)), and formazan metal complex dye (Reactive Blue 52 (RB52)). After the seven consecutive decolorization cycles, the decolorization was still 53, 78, and 67% of the initial dye for the Al-HRP-Gel, Al-Gel-HRP, and Chitosan-HRP immobilizate, respectively. The results obtained showed potential of otherwise neglected acidic HRP isoforms as a cost-effective biocatalyst with significant potential in wastewater dyestuff treatment.

Treatment of a simulated textile wastewater containing the Reactive Orange 16 azo dye by a combination of ozonation and moving-bed biofilm reactor: evaluating the performance, toxicity, and oxidation by-products.

PubMed

Castro, Francine D; Bassin, João Paulo; Dezotti, Márcia

2017-03-01

In this study, an aqueous solution containing the azo dye Reactive Orange 16 (RO16) was subjected to two sequential treatment processes, namely: ozonation and biological treatment in a moving-bed biofilm reactor (MBBR). The most appropriate ozonation pretreatment conditions for the biological process and the toxicity of the by-products resulting from RO16 ozone oxidation were evaluated. The results showed that more than 97 % of color removal from the dye solutions with RO16 concentrations ranging from 25 to 100 mg/L was observed in 5 min of ozone exposure. However, the maximum total organic carbon removal achieved by ozonation was only 48 %, indicating partial mineralization of the dye. Eleven intermediate organic compounds resulting from ozone treatment of RO16 solution were identified by LC/MS analyses at different contact times. The toxicity of the dye-containing solution decreased after 2 min of ozonation, but increased at longer contact times. The results further demonstrated that the ozonolysis products did not affect the performance of the subsequent MBBR, which achieved an average chemical oxygen demand (COD) and ammonium removal of 93 ± 1 and 97 ± 2 %, respectively. A second MBBR system fed with non-ozonated dye-containing wastewater was run in parallel for comparison purposes. This reactor also showed an appreciable COD (90 ± 1 %) and ammonium removal (97 ± 2 %), but was not effective in removing color, which remained practically invariable over the system. The use of short ozonation times (5 min) and a compact MBBR has shown to be effective for the treatment of the simulated textile wastewater containing the RO16 azo dye.

In-Vitro Analysis of the Effect of Constructional Parameters and Dye Class on the UV Protection Property of Cotton Knitted Fabrics.

PubMed

Kan, Chi-Wai; Au, Chui-Ha

2015-01-01

Cotton knitted fabrics were manufactured with different yarn types (conventional ring spun yarn and torque-free ring spun yarn) with different fibre types (combed cotton and combed Supima cotton) and yarn fineness (Ne30 and Ne40). These fabrics were then dyed with three types of dye (reactive, direct and sulphur dye) with three dye concentrations (0.1%, 1.0% and 5.0% on-weight of fabric (owf)) in three colours (red, yellow and blue). This study examined the impact of constructional parameters and dyeing on ultraviolet (UV) protection properties of cotton knitted fabric. In-vitro test with spectrophotometer was used for evaluating the UV protection property of dyed cotton knitted fabrics. Among the six parameters investigated, fineness of yarn and dye concentration were the most significant factors affecting UPF while the color effect is the least significant. Experimental results revealed that the UPF value of dyed fabrics made from combed cotton is generally higher than the combed Supima cotton since combed cotton is composed of shorter fibres which facilitate the blocking or absorption of UV radiation. Second, fabrics made with twist yarn (i.e. ring spun yarn) have higher UPF value than the corresponding ESTex one (i.e. torque-free yarn) in general since fabrics made with ring spun yarn tend to shrink during wet processing and so it is more compact. Third, the UPF value of fabrics made with 30Ne yarn was higher than the 40Ne one since it is thicker and has lower fabric porosity. Fourth, fabrics dyed with lower concentration of dye gave the lowest UPF. Fifth, the sulphur dyed samples performed worse than the reactive and direct dyed samples in terms of UV protection property. Sixth, there is no significant difference in UPF for red, yellow and blue coloured fabrics. Seventh, this study also demonstrated that lightness of fabric is negatively related to UV protection property.

In-Vitro Analysis of the Effect of Constructional Parameters and Dye Class on the UV Protection Property of Cotton Knitted Fabrics

PubMed Central

2015-01-01

Cotton knitted fabrics were manufactured with different yarn types (conventional ring spun yarn and torque-free ring spun yarn) with different fibre types (combed cotton and combed Supima cotton) and yarn fineness (Ne30 and Ne40). These fabrics were then dyed with three types of dye (reactive, direct and sulphur dye) with three dye concentrations (0.1%, 1.0% and 5.0% on-weight of fabric (owf)) in three colours (red, yellow and blue). This study examined the impact of constructional parameters and dyeing on ultraviolet (UV) protection properties of cotton knitted fabric. In-vitro test with spectrophotometer was used for evaluating the UV protection property of dyed cotton knitted fabrics. Among the six parameters investigated, fineness of yarn and dye concentration were the most significant factors affecting UPF while the color effect is the least significant. Experimental results revealed that the UPF value of dyed fabrics made from combed cotton is generally higher than the combed Supima cotton since combed cotton is composed of shorter fibres which facilitate the blocking or absorption of UV radiation. Second, fabrics made with twist yarn (i.e. ring spun yarn) have higher UPF value than the corresponding ESTex one (i.e. torque-free yarn) in general since fabrics made with ring spun yarn tend to shrink during wet processing and so it is more compact. Third, the UPF value of fabrics made with 30Ne yarn was higher than the 40Ne one since it is thicker and has lower fabric porosity. Fourth, fabrics dyed with lower concentration of dye gave the lowest UPF. Fifth, the sulphur dyed samples performed worse than the reactive and direct dyed samples in terms of UV protection property. Sixth, there is no significant difference in UPF for red, yellow and blue coloured fabrics. Seventh, this study also demonstrated that lightness of fabric is negatively related to UV protection property. PMID:26222792

Degradation kinetics of organic dyes in water by high voltage atmospheric air and modified air cold plasma.

PubMed

Pankaj, S K; Wan, Zifan; Colonna, William; Keener, Kevin M

2017-07-01

High voltage atmospheric cold plasma (HVACP) is a novel, non-thermal technology which has shown potential for degradation of various toxic components in wastewater. In this study, HVACP was used to examine the degradation kinetics of methyl red, crystal violet and fast green FCF dyes. HVACP discharge was found to be a source of reactive nitrogen and oxygen species. High voltage application completely degraded all dyes tested in less than 5 min treatment time. Plasma from modified gas (∼65% O 2 ) further reduced the treatment time by 50% vs. plasma from dry air. First order and Weibull models were fitted to the degradation data. The Weibull model was found better in explaining the degradation kinetics of all the treated dyes.

Force-field parametrization and molecular dynamics simulations of Congo red

NASA Astrophysics Data System (ADS)

Król, Marcin; Borowski, Tomasz; Roterman, Irena; Piekarska, Barbara; Stopa, Barbara; Rybarska, Joanna; Konieczny, Leszek

2004-01-01

Congo red, a diazo dye widely used in medical diagnosis, is known to form supramolecular systems in solution. Such a supramolecular system may interact with various proteins. In order to examine the nature of such complexes empirical force field parameters for the Congo red molecule were developed. The parametrization of bonding terms closely followed the methodology used in the development of the charmm22 force field, except for the calculation of charges. Point charges were calculated from a fit to a quantum mechanically derived electrostatic potential using the CHELP-BOW method. Obtained parameters were tested in a series of molecular dynamics simulations of both a single molecule and a micelle composed of Congo red molecules. It is shown that newly developed parameters define a stable minimum on the hypersurface of the potential energy and crystal and ab initio geometries and rotational barriers are well reproduced. Furthermore, rotations around C-N bonds are similar to torsional vibrations observed in crystals of diphenyl-diazene, which confirms that the flexibility of the molecule is correct. Comparison of results obtained from micelles molecular dynamics simulations with experimental data shows that the thermal dependence of micelle creation is well reproduced.

The effect of surfactant on pollutant biosorption of Trametes versicolor

NASA Astrophysics Data System (ADS)

Gül, Ülküye Dudu; Silah, Hülya; Akbaş, Halide; Has, Merve

2016-04-01

The major problem concerning industrial wastewater is treatment of dye and heavy metal containing effluents. Industrial effluents are also contained surfactants that are used as levelling, dispersing and wetting agents. The purpose of this study was to investigate the effect of surfactant on textile dye biosorption properties of a white rot fungus named Trametes versicolor. Reactive dyes are commonly used in textile industry because of their advantages such as brightness and excellent color fastness. A recative textile dye, called Everzol Black, was used in this study. The low-cost mollasses medium is used for fungal growth. The usage of mollases, the sugar refinery effluent as a source of energy and nutrients, gained importance because of reducing the cost and also reusing another waste. In biosorption process the effect of surfactant on dye removal properties of T. versicolor was examined as a function of pH, dye consentration and surfactant concentration. The results of this study showed that the surfactant enhanced the dye removal capacity of Trametes versicolor. The dye and surfactant molecules were interacted electrostatically and these electrostatic interactions improved dye removal properties of filamentous fungus T. versicolor. The results of this study recommended the use of surfactants as an inducer in textile wastewater treatment technologies.

Reactively sputtered nickel nitride as electrocatalytic counter electrode for dye- and quantum dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Soo Kang, Jin; Park, Min-Ah; Kim, Jae-Yup; Ha Park, Sun; Young Chung, Dong; Yu, Seung-Ho; Kim, Jin; Park, Jongwoo; Choi, Jung-Woo; Jae Lee, Kyung; Jeong, Juwon; Jae Ko, Min; Ahn, Kwang-Soon; Sung, Yung-Eun

2015-05-01

Nickel nitride electrodes were prepared by reactive sputtering of nickel under a N2 atmosphere at room temperature for application in mesoscopic dye- or quantum dot- sensitized solar cells. This facile and reliable method led to the formation of a Ni2N film with a cauliflower-like nanostructure and tetrahedral crystal lattice. The prepared nickel nitride electrodes exhibited an excellent chemical stability toward both iodide and polysulfide redox electrolytes. Compared to conventional Pt electrodes, the nickel nitride electrodes showed an inferior electrocatalytic activity for the iodide redox electrolyte; however, it displayed a considerably superior electrocatalytic activity for the polysulfide redox electrolyte. As a result, compared to dye-sensitized solar cells (DSCs), with a conversion efficiency (η) = 7.62%, and CdSe-based quantum dot-sensitized solar cells (QDSCs, η = 2.01%) employing Pt counter electrodes (CEs), the nickel nitride CEs exhibited a lower conversion efficiency (η = 3.75%) when applied to DSCs, but an enhanced conversion efficiency (η = 2.80%) when applied to CdSe-based QDSCs.

In silico analysis of Pycnoporus cinnabarinus laccase active site with toxic industrial dyes.

PubMed

Prasad, Nirmal K; Vindal, Vaibhav; Narayana, Siva Lakshmi; Ramakrishna, V; Kunal, Swaraj Priyaranjan; Srinivas, M

2012-05-01

Laccases belong to multicopper oxidases, a widespread class of enzymes implicated in many oxidative functions in various industrial oxidative processes like production of fine chemicals to bioremediation of contaminated soil and water. In order to understand the mechanisms of substrate binding and interaction between substrates and Pycnoporus cinnabarinus laccase, a homology model was generated. The resulted model was further validated and used for docking studies with toxic industrial dyes- acid blue 74, reactive black 5 and reactive blue 19. Interactions of chemical mediators with the laccase was also examined. The docking analysis showed that the active site always cannot accommodate the dye molecules, due to constricted nature of the active site pocket and steric hindrance of the residues whereas mediators are relatively small and can easily be accommodated into the active site pocket, which, thereafter leads to the productive binding. The binding properties of these compounds along with identification of critical active site residues can be used for further site-directed mutagenesis experiments in order to identify their role in activity and substrate specificity, ultimately leading to improved mutants for degradation of these toxic compounds.

Laccase-conjugated amino-functionalized nanosilica for efficient degradation of Reactive Violet 1 dye

NASA Astrophysics Data System (ADS)

Gahlout, Mayur; Rudakiya, Darshan M.; Gupte, Shilpa; Gupte, Akshaya

2017-08-01

Immobilization of enzyme with nanostructures enhances its ideal characteristics, which may allow the enzyme to become more stable and resistant. The present investigation deals with the formulation of laccase nanosilica conjugates to overcome the problems associated with its stability and reusability. Synthesized nanosilica and laccase nanoparticles were spherical shaped, with the mean size of 220 and 615 nm, respectively. Laccase nanoparticles had an optimum temperature of 55 °C and pH 4.0 for the oxidation of ABTS. Laccase nanoparticle retained 79% of residual activity till 20th cycle. It also showed 91% of its initial activity at lower temperatures even after 60 days. Laccase nanoparticles were applied for Reactive Violet 1 degradation wherein 96.76% of decolourization was obtained at pH 5.0 and 30 °C within 12 h. Toxicity studies on microbes and plants suggested that the degraded metabolites were less toxic than control dye. Thus, the method applied for immobilization increased storage stability and reusability of laccase, and therefore, it can be utilized for efficient degradation of azo dyes.

High-throughput screening of dye-ligands for chromatography.

PubMed

Kumar, Sunil; Punekar, Narayan S

2014-01-01

Dye-ligand-based chromatography has become popular after Cibacron Blue, the first reactive textile dye, found application for protein purification. Many other textile dyes have since been successfully used to purify a number of proteins and enzymes. While the exact nature of their interaction with target proteins is often unclear, dye-ligands are thought to mimic the structural features of their corresponding substrates, cofactors, etc. The dye-ligand affinity matrices are therefore considered pseudo-affinity matrices. In addition, dye-ligands may simply bind with proteins due to electrostatic, hydrophobic, and hydrogen-bonding interactions. Because of their low cost, ready availability, and structural stability, dye-ligand affinity matrices have gained much popularity. Choice of a large number of dye structures offers a range of matrices to be prepared and tested. When presented in the high-throughput screening mode, these dye-ligand matrices provide a formidable tool for protein purification. One could pick from the list of dye-ligands already available or build a systematic library of such structures for use. A high-throughput screen may be set up to choose best dye-ligand matrix as well as ideal conditions for binding and elution, for a given protein. The mode of operation could be either manual or automated. The technology is available to test the performance of dye-ligand matrices in small volumes in an automated liquid-handling workstation. Screening a systematic library of dye-ligand structures can help establish a structure-activity relationship. While the origins of dye-ligand chromatography lay in exploiting pseudo-affinity, it is now possible to design very specific biomimetic dye structures. High-throughput screening will be of value in this endeavor as well.

21 CFR 73.3121 - Poly(hydroxyethyl methacrylate)-dye copolymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

...-naphthalenedisulfonic acid, 4-amino-5-hydroxy-3,6-bis((4-((2-(sulfooxy)ethyl)sulfonyl)phenyl)azo)-tetrasodium salt] (CAS...)-] (CAS Reg. No. 60958-41-0); (5) Reactive Blue No. 19 [2-anthracene-sulfonic acid, 1-amino-9,10-dihydro-9...); (6) Reactive Blue No. 4 [2-anthracenesulfonic acid, 1-amino-4-(3-((4,6-dichloro-s-triazin-2-yl)amino...

21 CFR 73.3121 - Poly(hydroxyethyl methacrylate)-dye copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

...-naphthalenedisulfonic acid, 4-amino-5-hydroxy-3,6-bis((4-((2-(sulfooxy)ethyl)sulfonyl)phenyl)azo)-tetrasodium salt] (CAS...)-] (CAS Reg. No. 60958-41-0); (5) Reactive Blue No. 19 [2-anthracene-sulfonic acid, 1-amino-9,10-dihydro-9...); (6) Reactive Blue No. 4 [2-anthracenesulfonic acid, 1-amino-4-(3-((4,6-dichloro-s-triazin-2-yl)amino...

Computational Identification and Analysis of the Key Biosorbent Characteristics for the Biosorption Process of Reactive Black 5 onto Fungal Biomass

PubMed Central

Yang, Yu-Yi; Li, Ze-Li; Wang, Guan; Zhao, Xiao-Ping; Crowley, David E.; Zhao, Yu-Hua

2012-01-01

The performances of nine biosorbents derived from dead fungal biomass were investigated for their ability to remove Reactive Black 5 from aqueous solution. The biosorption data for removal of Reactive Black 5 were readily modeled using the Langmuir adsorption isotherm. Kinetic analysis based on both pseudo-second-order and Weber-Morris models indicated intraparticle diffusion was the rate limiting step for biosorption of Reactive Black 5 on to the biosorbents. Sorption capacities of the biosorbents were not correlated with the initial biosorption rates. Sensitivity analysis of the factors affecting biosorption examined by an artificial neural network model showed that pH was the most important parameter, explaining 22%, followed by nitrogen content of biosorbents (16%), initial dye concentration (15%) and carbon content of biosorbents (10%). The biosorption capacities were not proportional to surface areas of the sorbents, but were instead influenced by their chemical element composition. The main functional groups contributing to dye sorption were amine, carboxylic, and alcohol moieties. The data further suggest that differences in carbon and nitrogen contents of biosorbents may be used as a selection index for identifying effective biosorbents from dead fungal biomass. PMID:22442697

Biosorption of synthetic dyes (Direct Red 89 and Reactive Green 12) as an ecological refining step in textile effluent treatment.

PubMed

Guendouz, Samira; Khellaf, Nabila; Zerdaoui, Mostefa; Ouchefoun, Moussa

2013-06-01

With the use of cost-effective natural materials, biosorption is considered as an ecological tool that is applied worldwide for the remediation of pollution. In this study, we proposed Lemna gibba biomass (LGB), a lignocellulosic sorbent material, for the removal of two textile dyes, Direct Red 89 (DR-89) and Reactive Green 12 (RG-12). These azo dyes commonly used in dying operations of natural and synthetic fibres are the most important pollutants produced in textile industry effluents. For this purpose, batch biosorption experiments were carried out to assess the efficacy of LGB on dye treatment by evaluating the effect of contact time, biomass dosage, and initial dye concentration. The results indicated that the bioremoval efficiency of 5 mg L(-1) DR-89 and RG-12 reached approximately 100 % after 20 min of the exposure time; however, the maximum biosorption of 50 mg L(-1) DR-89 and 15 mg L(-1) RG-12 was determined to be about 60 and 47 %, respectively. Fourier transform infrared spectroscopy used to explain the sorption mechanism showed that the functional groups of carboxylic acid and hydroxyl played a major role in the retention of these pollutants on the biomass surface. The modelling results using Freundlich, Langmuir, Temkin, Elovich, and Dubini Radushkevich (D-R) isotherms demonstrated that the DR-89 biosorption process was better described with the Langmuir theory (R (2) =0.992) while the RG-12 biosorption process fitted well by the D-R isotherm equation (R (2) =0.988). The maximum biosorption capacity was found to be 20.0 and 115.5 mg g(-1) for DR-89 and RG-12, respectively, showing a higher ability of duckweed biomass for the bioremoval of the green dye. The thermodynamic study showed that the dye biosorption was a spontaneous and endothermic process. The efficacy of using duckweed biomass for the bioremoval of the two dyes was limited to concentrations ≤50 mg L(-1), indicating that L. gibba biomass may be suitable in the refining step of textile effluent treatment.

The Rhodium(II) Carbenoid Cyclization-Cycloaddition Cascade of α-Diazo Dihydroindolinones for the Synthesis of Novel Azapolycyclic Ring Systems‡

PubMed Central

England, Dylan B.; Eagan, James M.; Merey, Gokce; Anac, Olcay; Padwa, Albert

2008-01-01

Tandem carbonyl ylide formation-1,3-dipolar cycloaddition of α-diazo N-acetyl-tetrahydro-β-carbolin-1-one derivatives occur efficiently in the presence of a dirhodium catalyst to afford bimolecular cycloadducts in high yield. The Rh(II)-catalyzed reaction also takes place intramolecularly to give products derived from trapping of the carbonyl ylide dipole with a tethered alkene. The power of the intramolecular cascade sequence is that it rapidly assembles a pentacyclic ring system containing three new stereocenters and two adjacent quaternary centers stereospecifically in a single step and in high yield. PMID:18437248

N-(Pivaloyloxy)alkoxy-carbonyl Prodrugs of the Glutamine Antagonist 6-Diazo-5-oxo-l-norleucine (DON) as a Potential Treatment for HIV Associated Neurocognitive Disorders.

PubMed

Nedelcovych, Michael T; Tenora, Lukáš; Kim, Boe-Hyun; Kelschenbach, Jennifer; Chao, Wei; Hadas, Eran; Jančařík, Andrej; Prchalová, Eva; Zimmermann, Sarah C; Dash, Ranjeet P; Gadiano, Alexandra J; Garrett, Caroline; Furtmüller, Georg; Oh, Byoungchol; Brandacher, Gerald; Alt, Jesse; Majer, Pavel; Volsky, David J; Rais, Rana; Slusher, Barbara S

2017-08-24

Aberrant excitatory neurotransmission associated with overproduction of glutamate has been implicated in the development of HIV-associated neurocognitive disorders (HAND). The glutamine antagonist 6-diazo-5-oxo-l-norleucine (DON, 14) attenuates glutamate synthesis in HIV-infected microglia/macrophages, offering therapeutic potential for HAND. We show that 14 prevents manifestation of spatial memory deficits in chimeric EcoHIV-infected mice, a model of HAND. 14 is not clinically available, however, because its development was hampered by peripheral toxicities. We describe the synthesis of several substituted N-(pivaloyloxy)alkoxy-carbonyl prodrugs of 14 designed to circulate inert in plasma and be taken up and biotransformed to 14 in the brain. The lead prodrug, isopropyl 6-diazo-5-oxo-2-(((phenyl(pivaloyloxy)methoxy)carbonyl)amino)hexanoate (13d), was stable in swine and human plasma but liberated 14 in swine brain homogenate. When dosed systemically in swine, 13d provided a 15-fold enhanced CSF-to-plasma ratio and a 9-fold enhanced brain-to-plasma ratio relative to 14, opening a possible clinical path for the treatment of HAND.

Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions.

PubMed

Filimonov, Valeriy O; Dianova, Lidia N; Galata, Kristina A; Beryozkina, Tetyana V; Novikov, Mikhail S; Berseneva, Vera S; Eltsov, Oleg S; Lebedev, Albert T; Slepukhin, Pavel A; Bakulev, Vasiliy A

2017-04-21

High yield solvent-base-controlled, transition metal-free synthesis of 4,5-functionalized 1,2,3-thiadiazoles and 1,2,3-triazoles from 2-cyanothioacetamides and sulfonyl azides is described. Under diazo transfer conditions in the presence of a base in an aprotic solvent 2-cyanothioacetamides operating as C-C-S building blocks produce 5-amino-4-cyano-1,2,3-thiadiazoles exclusively. The use of alkoxide/alcohol system completely switches the reaction course due to the change of one of the reaction centers in the 2-cyanothioacetamide (C-C-N building block) resulting in the formation of 5-sulfonamido-1,2,3-triazole-4-carbothioamide sodium salts as the only products. The latter serve as good precursors for 5-amino-1,2,3-thiadiazole-4-carboximidamides, the products of Cornforth-type rearrangement occurring in neutral protic medium or under acid conditions. According to DFT calculations (B3LYP/6-311+G(d,p)) the rearrangement proceeds via intermediate formation of a diazo compound, and can be catalyzed by acids via the protonation of oxygen atom of the sulfonamide group.

Adsorption of a reactive dye on chemically modified activated carbons--influence of pH.

PubMed

Orfão, J J M; Silva, A I M; Pereira, J C V; Barata, S A; Fonseca, I M; Faria, P C C; Pereira, M F R

2006-04-15

The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and basic properties, without changing its textural parameters significantly. Different techniques (N2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H2 flow at 700 degrees C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH(pzc) of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.

Comparison of Hydrazone Heterobifunctional Crosslinking Agents for Reversible Conjugation of Thiol-Containing Chemistry

PubMed Central

Christie, R. James; Anderson, Diana J.; Grainger, David W.

2010-01-01

Reversible covalent conjugation chemistries that allow site- and condition-specific coupling and uncoupling reactions are attractive components in nanotechnologies, bioconjugation methods, imaging and drug delivery systems. Here, we compare three heterobifunctional crosslinkers, containing both thiol- and amine- reactive chemistry, to form pH-labile hydrazones with hydrazide derivatives of the known and often published water-soluble polymer, poly[N-(2-hydroxypropyl methacrylamide)] (pHPMA), while subsequently coupling thiol-containing molecules to the crosslinker via maleimide addition. Two novel crosslinkers were prepared from the popular heterobifunctional crosslinking agent, succinimidyl-4-(N-maleimidomethyl) cyclohexane-1-carboxylate (SMCC), modified to contain either terminal aldehyde groups (i.e., 1-(N-3-propanal)-4-(N-maleimidomethyl) cyclohexane carboxamide, PMCA) or methylketone groups (i.e., 1-(N-3-butanone)-4-(N-maleimidomethyl) cyclohexane carboxamide, BMCA). A third crosslinking agent was the commercially available N-4-acetylphenyl maleimide (APM). PMCA and BMCA exhibited excellent reactivity towards hydrazide-derivatized pHPMA with essentially complete hydrazone conjugation to polymer reactive sites, while APM coupled only ~ 60% of available reactive sites on the polymer despite a 3-fold molar excess relative to polymer hydrazide groups. All polymer hydrazone conjugates bearing these bifunctional agents were then further reacted with thiol-modified tetramethylrhodamine dye, confirming crosslinker maleimide reactivity after initial hydrazone polymer conjugation. Incubation of dye-labeled polymer conjugates in phosphate buffered saline at 37°C showed that hydrazone coupling resulting from APM exhibited the greatest difference in stability between pH 7.4 and 5.0, with hydrolysis and dye release increased at pH 5.0 over a 24hr incubation period. Polymer conjugates bearing hydrazones formed from crosslinker BMCA exhibited intermediate stability with hydrolysis much greater at pH 5.0 at early time points, but hydrolysis at pH 7.4 was significant after 5 hrs. Hydrazones formed with the PMCA crosslinker showed no difference in release rates at pH 7.4 and 5.0. PMID:20695431

Preparation of ZnO Photocatalyst for the Efficient and Rapid Photocatalytic Degradation of Azo Dyes.

PubMed

Chen, Xiaoqing; Wu, Zhansheng; Liu, Dandan; Gao, Zhenzhen

2017-12-01

Zinc oxide (ZnO) photocatalysts were synthesized by sol-gel method using zinc acetate as precursor for degradation of azo dyes under UV irradiation. The resultant samples were characterized by different techniques, such as XRD, SEM, and EDX. The influence of preparation conditions such as calcination temperature and composite ratio on the degradation of methyl orange (MO) was investigated. ZnO prepared with a composite ratio of 4:1 and calcination temperature of 400 °C exhibited 99.70% removal rate for MO. The effect of operation parameters on the degradation was also studied. Results showed that the removal rate of azo dyes increased with the increased dosage of catalyst and decreased initial concentration of azo dyes and the acidic condition is favorable for degradation. Furthermore, the kinetics and scavengers of the reactive species during the degradation were also investigated. It was found that the degradation of azo dyes fitted the first-order kinetics and superoxide ions were the main species. The proposed photocatalyst can efficiently and rapidly degrade azo dyes; thus, this economical and environment-friendly photocatalyst can be applied to the treatment of wastewater contaminated with synthetic dyes.

Efficiency Improvement of Some Agricultural Residue Modified Materials for Textile Dyes Absorption

NASA Astrophysics Data System (ADS)

Boonsong, P.; Paksamut, J.

2018-03-01

In this work, the adsorption efficiency was investigated of some agricultural residue modified materials as natural bio-adsorbents which were rice straw (Oryza sativa L.) and pineapple leaves (Ananas comosus (L.) Merr.) for the removal of textile dyes. Reactive dyes were used in this research. The improvement procedure of agricultural residue materials properties were alkali-acid modification with sodium hydroxide solution and hydrochloric acid solution. Adsorption performance has been investigated using batch experiments. Investigated adsorption factors consisted of adsorbent dose, contact time, adsorbent materials and pH of solution. The results were found that rice straw had higher adsorption capacity than pineapple leaves. The increasing of adsorption capacity depends on adsorbent dose and contact time. Moreover, the optimum pH for dye adsorption was acidic range because lowering pH increased the positively charges on the adsorbent surface which could be attacked by negatively charge of acid dyes. The agricultural residue modified materials had significant dye removal efficiency which these adsorbents could be used for the treatment of textile effluent in industries.

Simultaneous photocatalytic and microbial degradation of dye-containing wastewater by a novel g-C3N4-P25/photosynthetic bacteria composite

PubMed Central

Zhang, Xinying; Wu, Yan; Xiao, Gao; Tang, Zhenping; Wang, Meiyin; Liu, Fuchang; Zhu, Xuefeng

2017-01-01

Azo dyes are very resistant to light-induced fading and biodegradation. Existing advanced oxidative pre-treatment methods based on the generation of non-selective radicals cannot efficiently remove these dyes from wastewater streams, and post-treatment oxidative dye removal is problematic because it may leave many byproducts with unknown toxicity profiles in the outgoing water, or cause expensive complete mineralization. These problems could potentially be overcome by combining photocatalysis and biodegradation. A novel visible-light-responsive hybrid dye removal agent featuring both photocatalysts (g-C3N4-P25) and photosynthetic bacteria encapsulated in calcium alginate beads was prepared by self-assembly. This system achieved a removal efficiency of 94% for the dye reactive brilliant red X-3b and also reduced the COD of synthetic wastewater samples by 84.7%, successfully decolorized synthetic dye-contaminated wastewater and reduced its COD, demonstrating the advantages of combining photocatalysis and biocatalysis for wastewater purification. The composite apparently degrades X-3b by initially converting the dye into aniline and phenol derivatives whose aryl moieties are then attacked by free radicals to form alkyl derivatives, preventing the accumulation of aromatic hydrocarbons that might suppress microbial activity. These alkyl intermediates are finally degraded by the photosynthetic bacteria. PMID:28273118

Amine-Reactive Fluorene Probes: Synthesis, Optical Characterization, Bioconjugation, and Two-Photon Fluorescence Imaging

PubMed Central

2008-01-01

With the increasing demand for confocal and two-photon fluorescence imaging, the availability of reactive probes that possess high two-photon absorptivity, high fluorescence quantum yield, and high photostability is of paramount importance. To address the demand for better-performing probes, we prepared two-photon absorbing amine-reactive fluorenyl-based probes 2-(9,9-bis(2-(2-methoxyethoxy)ethyl)-2-isothiocyanato-9H-fluoren-7-yl)benzothiazole (1) and 2-(4-(2-(9,9-bis(2-(2-ethoxyethoxy)ethyl)-2-isothiocyanato-9H-fluoren-7-yl)vinyl)phenyl)benzothiazole (2), incorporating the isothiocyanate as a reactive linker. Probe design was augmented by integrating high optical nonlinearities, increased hydrophilicity, and coupling with reactive functional groups for specific targeting of biomolecules, assuring a better impact on two-photon fluorescence microscopy (2PFM) imaging. The isothiocyanate (NCS) derivatives were conjugated with cyclic peptide RGDfK and Reelin protein. The study of the chemical and photophysical properties of the new labeling reagents, as well as the conjugates, is described. The conjugates displayed high chemical stability and photostability. The NCS derivatives had low fluorescence quantum yields, while their bioconjugates exhibited high fluorescence quantum yields, essentially “lighting up” after conjugation. Conventional and 2PFM imaging and fluorescence lifetime imaging (FLIM) of HeLa, NT2, and H1299 cells, incubated with two-photon absorbing amine-reactive probe (1), RGDfK-dye conjugate (7), and Reelin-dye conjugate (6), was demonstrated. PMID:19090700

The effect of the textile industry dye bath additive EDTMPA on colour removal characteristics by ozone oxidation.

PubMed

Olmez, T; Kabdaşli, I; Tünay, O

2007-01-01

In this study, the effects of the phosphonic acid based sequestering agent EDTMPA used in the textile dye baths on colour and organic matter removal by ozone oxidation was experimentally investigated. Procion Navy HEXL dyestuff that has been commonly used for the reactive dyeing of cellulose fibers was selected as the model component. The organic matter oxidation by ozone was determined to obey the pseudo-first order kinetics as they are treated singly or in combination. COD removal rates obtained from pseudo-first order reaction kinetics showed that oxidation of Navy HEXL alone (0.0947 L/min) was faster than that of EDTMPA (0.0171 L/min) and EDTMPA with dye (0.0155 L/min) at pH 3.0. It was also found that reaction rates of single EDTMPA removal and EDTMPA and dye mixture removal increased as the reaction pH was increased from 3.0 to 10.5.

Effectiveness of Rice Agricultural Waste, Microbes and Wetland Plants in the Removal of Reactive Black-5 Azo Dye in Microcosm Constructed Wetlands.

PubMed

Saba, Beenish; Jabeen, Madeeha; Khalid, Azeem; Aziz, Irfan; Christy, Ann D

2015-01-01

Azo dyes are commonly generated as effluent pollutants by dye using industries, causing contamination of surface and ground water. Various strategies are employed to treat such wastewater; however, a multi-faceted treatment strategy could be more effective for complete removal of azo dyes from industrial effluent than any single treatment. In the present study, rice husk material was used as a substratum in two constructed wetlands (CWs) and augmented with microorganisms in the presence of wetland plants to effectively treat dye-polluted water. To evaluate the efficiency of each process the study was divided into three levels, i.e., adsorption of dye onto the substratum, phytoremediation within the CW and then bioremediation along with the previous two processes in the augmented CW. The adsorption process was helpful in removing 50% dye in presence of rice husk while 80% in presence of rice husk biocahr. Augmentation of microorganisms in CW systems has improved dye removal efficiency to 90%. Similarly presence of microorganisms enhanced removal of total nitrogen (68% 0 and Total phosphorus (75%). A significant improvement in plant growth was also observed by measuring plant height, number of leaves and leave area. These findings suggest the use of agricultural waste as part of a CW substratum can provide enhanced removal of textile dyes.

Decolorization of adsorbed textile dyes by developed consortium of Pseudomonas sp. SUK1 and Aspergillus ochraceus NCIM-1146 under solid state fermentation.

PubMed

Kadam, Avinash A; Telke, Amar A; Jagtap, Sujit S; Govindwar, Sanjay P

2011-05-15

The objective of this study was to develop consortium using Pseudomonas sp. SUK1 and Aspergillus ochraceus NCIM-1146 to decolorize adsorbed dyes from textile effluent wastewater under solid state fermentation. Among various agricultural wastes rice bran showed dye adsorption up to 90, 62 and 80% from textile dye reactive navy blue HE2R (RNB HE2R) solution, mixture of textile dyes and textile industry wastewater, respectively. Pseudomonas sp. SUK1 and A. ochraceus NCIM-1146 showed 62 and 38% decolorization of RNB HE2R adsorbed on rice bran in 24h under solid state fermentation. However, the consortium of Pseudomonas sp. SUK1 and A. ochraceus NCIM-1146 (consortium-PA) showed 80% decolorization in 24h. The consortium-PA showed effective ADMI removal ratio of adsorbed dyes from textile industry wastewater (77%), mixture of textile dyes (82%) and chemical precipitate of textile dye effluent (CPTDE) (86%). Secretion of extracellular enzymes such as laccase, azoreductase, tyrosinase and NADH-DCIP reductase and their significant induction in the presence of adsorbed dye suggests their role in the decolorization of RNB HE2R. GCMS and HPLC analysis of product suggests the different fates of biodegradation of RNB HE2R when used Pseudomonas sp. SUK1, A. ochraceus NCIM-1146 and consortium PA. Copyright © 2011 Elsevier B.V. All rights reserved.

Tolerance to a Hair Dye Product Containing 2-Methoxymethyl-P-Phenylenediamine in an Ethnically Diverse Population of P-Phenylenediamine-Allergic Individuals.

PubMed

Zahir, Amir; Kindred, Chesahna; Blömeke, Brunhilde; Goebel, Carsten; Gaspari, Anthony A

Allergic contact dermatitis after exposure to p-phenylenediamine (PPD)-containing hair dye products is a common and important clinical problem. Because there is a high rate of cross-elicitation of allergic contact dermatitis to other important hair dye products (such as p-toluene diamine and other aminophenol hair dyes) in PPD-allergic patients, safer alternative dyes with excellent hair coloring options are needed. This study aimed to study tolerance to Me-PPD in a PPD-allergic cohort. Twenty ethnically diverse volunteers with a history of contact dermatitis to hair dyes or other PPD-containing chemicals and positive patch test results to 1% PPD in petrolatum were recruited to study their immediate and delayed skin reactivity to PPD, vehicle control, and 2-methoxy-methyl-PPD (Me-PPD) using the allergy alert test (simulating hair dyeing conditions) on volar forearm skin. This test is a short-contact open patch test. The Me-PPD may offer a safer alternative for PPD-allergic patients with an absent or reduced elicitation response in the allergy alert test simulating hair dye use conditions. The absent or reduced response to Me-PPD diagnosed using the allergy alert test has been shown to help reduce the possibility of moderate to severe cross-elicitation reactions among consumers during hair dyeing.

Reuse of waste beer yeast sludge for biosorptive decolorization of reactive blue 49 from aqueous solution.

PubMed

Wang, Baoe; Guo, Xiu

2011-06-01

Reactive blue 49 was removed from aqueous solution by biosorption using powder waste sludge composed of Saccharomyces cerevisiae from the beer-brewing industry. The effect of initial pH, temperature and the biosorption thermodynamics, equilibrium, kinetics was investigated in this study. It was found that the biosorption capacity was at maximum at initial pH 3, that the effect of temperature on biosorption of reactive blue 49 was only slight in relation to the large biosorption capacity (25°C, 361 mg g(-1)) according as the biosorption capacity decreased only 43 mg g(-1) at the temperature increased from 25 to 50°C. The biosorption was spontaneous, exothermic in nature and the dye molecules movements decreased slightly in random at the solid/liquid interface during the biosorption of dye on biosorbents. The biosorption equilibrium data could be described by Freundich isotherm model. The biosorption rates were found to be consistent with a pseudo-second-order kinetics model. The functional group interaction analysis between waste beer yeast sludge and reactive blue 49 by the aid of Fourier transform infrared (abbr. FTIR) spectroscopy indicated that amino components involved in protein participated in the biosorption process, which may be achieved by the mutual electrostatic adsorption process between the positively charged amino groups in waste beer yeast sludge with negatively charged sulfonic groups in reactive blue 49.

Characterizing Reactive Flow Paths in Fractured Cement

NASA Astrophysics Data System (ADS)

Wenning, Q. C.; Huerta, N. J.; Hesse, M. A.; Bryant, S. L.

2011-12-01

Geologic carbon sequestration can be a viable method for reducing anthropogenic CO2 flux into the atmosphere. However, the technology must be economically feasible and pose acceptable risk to stakeholders. One key risk is CO2 leakage out of the storage reservoir. Potential driving forces for leakage are the overpressure due to CO2 injection and the buoyancy of free phase CO2. Potential hazards of leakage are contamination of Underground Sources of Drinking Water or the atmosphere and would be deemed an unacceptable risk. Wells potentially provide a fast path for leakage from the reservoir. While the well's cement casing is reactive with CO2 and CO2-saturated brine, the low cement matrix permeability and slow diffusion rate make it unlikely that CO2 will escape through a properly constructed wellbore. However, highly permeable fractures with micrometer scale apertures can occur in cement casings. Reactions that occur in the flow in these fractures can either be self-limiting or self-enhancing. Therefore, understanding the reactive flow is critical to understanding of leakage evolution through these fractures. The goal of our work is to characterize the modification of the flow paths in the fracture due to reaction with acidic brine. With this aim we have characterized both the initial flow path of un-reactive flow and the final flow path after introduction of low-pH acid along the same fracture. Class H cement cores 3-6 cm in length and 2.5 cm diameter are created and a single natural and unique fracture is produced in each core using the Brazilian method. Our experimental fluid is injected at a constant rate into the cement core housed in a Hassler Cell under confining pressure. A solution of red dye and deionized water is pumped through the fracture to stain the un-reactive flow paths. Deionized water is then pumped through the core to limit diffusion of the dye into non-flowing portions of the fracture. After staining the initial flow path, low pH water due to hydrochloric acid (HCL), is pumped through the core at the same rate as the dye. The low pH water is used as a proxy for acidic CO2-saturated brine. Both staining from the un-reactive dye and acid produce visible permanent color alterations on the cement fracture plane. Results show that nearly the entire fracture width is stained by the red dye, with only a few asperities un-dyed. However the low pH HCl forms restricted reacted channels that are a subset of the area open to un-reactive flow, occupying only 10-50% of the entire fracture width. Low pH HCl is believed to be the driving force for the reaction that causes channeling. As acid flows through the fracture, calcium is stripped from the low pH high velocity flow front and precipitates along of the edges of the channel where pH is higher due to the lower flow velocities outside the channel. It is hypothesized that this mineral precipitation restricts the flow into localized channels within the plane of fractures having apertures of tens of micrometers. Reactions restrict the flow path to a smaller fraction of the surface, which may be an indication of self-limiting behavior.

Gold-Catalyzed Formal [4+1]/[4+3] Cycloadditions of Diazo Esters with Triazines.

PubMed

Zhu, Chenghao; Xu, Guangyang; Sun, Jiangtao

2016-09-19

Reported herein is the unprecedented gold-catalyzed formal [4+1]/[4+3] cycloadditions of diazo esters with hexahydro-1,3,4-triazines, thus providing five- and seven-membered heterocycles in moderate to high yields under mild reaction conditions. These reactions feature the use of a gold complex to accomplish the diverse annulations and the first example of the involvement of a gold metallo-enolcarbene in a cycloaddition. It is also the first utilization of stable triazines as formal dipolar adducts in the carbene-involved cycloadditions. Mechanistic investigations reveal that the triazines reacted directly, rather than as formaldimine precursors, in the reaction process. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conformations and charge distributions of diazocyclopropanes

NASA Astrophysics Data System (ADS)

Borges, Itamar, Jr.

Three diazo-substituted cyclopropane compounds, which have been suggested as new potential high energy compounds, were studied employing the B3LYP-DFT/6-31G(d,p) method. Geometries were optimized. Distributed multipole analysis, computed from the B3LYP-DFT/6-31G(d,p) density matrix, was used to describe the details of the molecular charge distribution of the three molecules. It was verified that electron withdrawing from the C ring atoms and charge build-up on the N atoms bonded to the ring increased with the number of diazo groups. These effects were related to increased sensitivity to impact and easiness of C bond N bond breaking in the three compounds.

Rapid cycloaddition of a diazo group with an unstrained dipolarophile.

PubMed

Aronoff, Matthew R; Gold, Brian; Raines, Ronald T

2016-06-01

The cycloaddition of a diazoacetamide with ethyl 4,4,4-trifluorocrotonate proceeds with k = 0.1 M -1 s -1 . This second-order rate constant rivals those of optimized strain-promoted azide- alkyne cycloadditions, even though the reaction does not release strain. The regioselectivity and a computational distortion/interaction analysis of the reaction energetics are consistent with the formation of an N-H…F-C hydrogen bond in the transition state and the electronic character of the trifluorocrotonate. Analogous reactions with an azidoacetamide dipole or with an acrylate or crotonate dipolarophile were much slower. These findings suggest a new strategy for the design of diazo-selective reagents for chemical biology.

A comparison of different activated carbon performances on catalytic ozonation of a model azo reactive dye.

PubMed

Gül, S; Eren, O; Kır, S; Onal, Y

2012-01-01

The objective of this study is to compare the performances of catalytic ozonation processes of two activated carbons prepared from olive stone (ACOS) and apricot stone (ACAS) with commercial ones (granular activated carbon-GAC and powder activated carbon-PAC) in degradation of reactive azo dye (Reactive Red 195). The optimum conditions (solution pH and amount of catalyst) were investigated by using absorbencies at 532, 220 and 280 nm wavelengths. Pore properties of the activated carbon (AC) such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption. The highest BET surface area carbon (1,275 m(2)/g) was obtained from ACOS with a particle size of 2.29 nm. After 2 min of catalytic ozonation, decolorization performances of ACOS and ACAS (90.4 and 91.3%, respectively) were better than that of GAC and PAC (84.6 and 81.2%, respectively). Experimental results showed that production of porous ACs with high surface area from olive and apricot stones is feasible in Turkey.

On the behavior of reduced graphene oxide based electrodes coated with dispersed platinum by alternate current methods in the electrochemical degradation of reactive dyes.

PubMed

Del Río, A I; García, C; Molina, J; Fernández, J; Bonastre, J; Cases, F

2017-09-01

The electrochemical behavior of different carbon-based electrodes with and without nanoparticles of platinum electrochemically dispersed on their surface has been studied. Among others, reduced graphene oxide based electrodes was used to determine the best conditions for the decolorization/degradation of the reactive dye C.I. Reactive Orange 4 in sulfuric medium. Firstly, the electrochemical behavior was evaluated by cyclic voltammetry. Secondly, different electrolyses were performed using two cell configurations: cell with anodic and cathodic compartments separated (divided configuration) and without any separation (undivided configuration). The best results were obtained when reduced graphene oxide based anodes were used. The degree of decolorization was monitored by spectroscopic methods and high performance liquid chromatography. It was found that all of them followed pseudo-first order kinetics. When reduced graphene oxide-based electrodes coated with dispersed platinum by alternate current methods electrodes were used, the lowest energy consumption and the higher decolorization kinetics rate were obtained. Scanning Electronic Microscopy was used to observe the morphological surface differences. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biodecoloration of Reactive Black 5 by the methylotrophic yeast Candida boidinii MM 4035.

PubMed

Martorell, María M; Pajot, Hipólito F; Ahmed, Pablo M; de Figueroa, Lucía I C

2017-03-01

Azo dyes are extensively used in textile dyeing and other industries. Effluents of dying industries are specially colored and could cause severe damage to the environment. The anaerobic treatment of textile dying effluents is nowadays the preferred option, but it could generate carcinogenic aromatic amines. Recently, yeasts have become a promising alternative, combining unicellular growth with oxidative mechanisms. This work reports the characterization of the first methylotrophic yeast with dye decolorizing ability, Candida boidinii MM 4035 and some insights into its decoloration mechanism. The analysis of two selected media revealed a possible two stages mechanism of Reactive Black 5 decoloration. In glucose poor media, decoloration is incomplete and only the first stage proceeds, leading to the accumulation of a purple compound. In media with higher glucose concentrations, the yeast is able to decolorize totally an initial concentration of 200mg/L. The entire process is co-metabolic, being largely dependent on glucose concentration but being able to proceed with several nitrogen sources. Manganese dependent peroxidase but not laccase activity could be detected during decoloration. Aromatic amines do not accumulate in culture media, supporting an oxidative decoloration mechanism of unknown ecophysiological relevance. Copyright © 2016. Published by Elsevier B.V.

Deposition of Visible Light Active Photocatalytic Bismuth Molybdate Thin Films by Reactive Magnetron Sputtering

PubMed Central

Ratova, Marina; Kelly, Peter J.; West, Glen T.; Xia, Xiaohong; Gao, Yun

2016-01-01

Bismuth molybdate thin films were deposited by reactive magnetron co-sputtering from two metallic targets in an argon/oxygen atmosphere, reportedly for the first time. Energy dispersive X-ray spectroscopy (EDX) analysis showed that the ratio of bismuth to molybdenum in the coatings can be effectively controlled by varying the power applied to each target. Deposited coatings were annealed in air at 673 K for 30 min. The crystalline structure was assessed by means of Raman spectroscopy and X-ray diffraction (XRD). Oxidation state information was obtained by X-ray photoelectron spectroscopy (XPS). Photodegradation of organic dyes methylene blue and rhodamine B was used for evaluation of the photocatalytic properties of the coatings under a visible light source. The photocatalytic properties of the deposited coatings were then compared to a sample of commercial titanium dioxide-based photocatalytic product. The repeatability of the dye degradation reactions and photocatalytic coating reusability are discussed. It was found that coatings with a Bi:Mo ratio of approximately 2:1 exhibited the highest photocatalytic activity of the coatings studied; its efficacy in dye photodegradation significantly outperformed a sample of commercial photocatalytic coating. PMID:28787867

Extraction and Application of Laccases from Shimeji Mushrooms (Pleurotus ostreatus) Residues in Decolourisation of Reactive Dyes and a Comparative Study Using Commercial Laccase from Aspergillus oryzae

PubMed Central

Teixeira, Ricardo Sposina S.; Pereira, Patrícia Maia; Ferreira-Leitão, Viridiana S.

2010-01-01

Oxidases are able to degrade organic pollutants; however, high costs associated with biocatalysts production still hinder their use in environmental biocatalysis. Our study compared the action of a commercial laccase from Aspergillus oryzae and a rich extract from Pleurotus ostreatus cultivation residues in decolourisation of reactive dyes: Drimaren Blue X-3LR (DMBLR), Drimaren Blue X-BLN (DMBBLN), Drimaren Rubinol X-3LR (DMR), and Drimaren Blue C-R (RBBR). The colour removal was evaluated by considering dye concentration, reaction time, absence or presence of the mediator ABTS (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), and the source of laccase. The presence of ABTS was essential for decolourisation of DMR (80–90%, 1 h) and RBBR (80–90%, 24 h) with both laccases. The use of ABTS was not necessary in reactions containing DMBLR (85–97%, 1 h) and DMBBLN (63–84%, 24 h). The decolourisation of DMBBLN by commercial laccase showed levels near 60% while the crude extract presented 80% in 24 h. PMID:21052547

Removal of reactive red-120 and 4-(2-pyridylazo) resorcinol from aqueous samples by Fe3O4 magnetic nanoparticles using ionic liquid as modifier.

PubMed

Absalan, Ghodratollah; Asadi, Mozaffar; Kamran, Sedigheh; Sheikhian, Leila; Goltz, Douglas M

2011-08-30

The nanoparticles of Fe(3)O(4) as well as the binary nanoparticles of ionic liquid and Fe(3)O(4) (IL-Fe(3)O(4)) were synthesized for removal of reactive red 120 (RR-120) and 4-(2-pyridylazo) resorcinol (PAR) as model azo dyes from aqueous solutions. The mean size and the surface morphology of the nanoparticles were characterized by TEM, DLS, XRD, FTIR and TGA techniques. Adsorption of RR-120 and PAR was studied in a batch reactor at different experimental conditions such as nanoparticle dosage, dye concentration, pH of the solution, ionic strength, and contact time. Experimental results indicated that the IL-Fe(3)O(4) nanoparticles had removed more than 98% of both dyes under the optimum operational conditions of a dosage of 60mg, a pH of 2.5, and a contact time of 2min when initial dyes concentrations of 10-200mg L(-1) were used. The maximum adsorption capacity of IL-Fe(3)O(4) was 166.67 and 49.26mg g(-1) for RR-120 and PAR, respectively. The isotherm experiments revealed that the Langmuir model attained better fits to the equilibrium data than the Freundlich model. The Langmuir adsorption constants were 5.99 and 3.62L mg(-1) for adsorptions of RR-120 and PAR, respectively. Both adsorption processes were endothermic and dyes could be desorbed from IL-Fe(3)O(4) by using a mixed NaCl-acetone solution and adsorbent was reusable. Copyright © 2011 Elsevier B.V. All rights reserved.

Computational and experimental analysis identified 6-diazo-5-oxonorleucine as a potential agent for treating infection by Plasmodium falciparum.

PubMed

Plaimas, Kitiporn; Wang, Yulin; Rotimi, Solomon O; Olasehinde, Grace; Fatumo, Segun; Lanzer, Michael; Adebiyi, Ezekiel; König, Rainer

2013-12-01

Plasmodium falciparum (PF) is the most severe malaria parasite. It is developing resistance quickly to existing drugs making it indispensable to discover new drugs. Effective drugs have been discovered targeting metabolic enzymes of the parasite. In order to predict new drug targets, computational methods can be used employing database information of metabolism. Using this data, we performed recently a computational network analysis of metabolism of PF. We analyzed the topology of the network to find reactions which are sensitive against perturbations, i.e., when a single enzyme is blocked by drugs. We now used a refined network comprising also the host enzymes which led to a refined set of the five targets glutamyl-tRNA (gln) amidotransferase, hydroxyethylthiazole kinase, deoxyribose-phophate aldolase, pseudouridylate synthase, and deoxyhypusine synthase. It was shown elsewhere that glutamyl-tRNA (gln) amidotransferase of other microorganisms can be inhibited by 6-diazo-5-oxonorleucine. Performing a half maximal inhibitory concentration (IC50) assay, we showed, that 6-diazo-5-oxonorleucine is also severely affecting viability of PF in blood plasma of the human host. We confirmed this by an in vivo study observing Plasmodium berghei infected mice. Copyright © 2013 Elsevier B.V. All rights reserved.

Microcolumn studies of dye adsorption onto manganese oxides modified diatomite.

PubMed

Al-Ghouti, M A; Khraisheh, M A M; Ahmad, M N; Allen, S J

2007-07-19

The method described here cannot fully replace the analysis of large columns by small test columns (microcolumns). The procedure, however, is suitable for speeding up the determination of adsorption parameters of dye onto the adsorbent and for speeding up the initial screening of a large adsorbent collection that can be tedious if a several adsorbents and adsorption conditions must be tested. The performance of methylene blue (MB), a basic dye, Cibacron reactive black (RB) and Cibacron reactive yellow (RY) was predicted in this way and the influence of initial dye concentration and other adsorption conditions on the adsorption behaviour were demonstrated. On the basis of the experimental results, it can be concluded that the adsorption of RY onto manganese oxides modified diatomite (MOMD) exhibited a characteristic "S" shape and can be simulated effectively by the Thomas model. It is shown that the adsorption capacity increased as the initial dye concentration increased. The increase in the dye uptake capacity with the increase of the adsorbent mass in the column was due to the increase in the surface area of adsorbent, which provided more binding sites for the adsorption. It is shown that the use of high flow rates reduced the time that RY in the solution is in contact with the MOMD, thus allowing less time for adsorption to occur, leading to an early breakthrough of RY. A rapid decrease in the column adsorption capacity with an increase in particle size with an average 56% reduction in capacity resulting from an increase in the particle size from 106-250 microm to 250-500 microm. The experimental data correlated well with calculated data using the Thomas equation and the bed depth-service time (BDST) equation. Therefore, it might be concluded that the Thomas equation and the BDST equations can produce accurate predication for variation of dye concentration, mass of the adsorbent, flow rate and particle size. In general, the values of adsorption isotherm capacity obtained in a batch system show the maximum values and are considerably higher than those obtained in a fixed-bed.

Textile dye degradation using nano zero valent iron: A review.

PubMed

Raman, Chandra Devi; Kanmani, S

2016-07-15

Water soluble unfixed dyes and inorganic salts are the major pollutants in textile dyeing industry wastewater. Existing treatment methods fail to degrade textile dyes and have limitations too. The inadequate treatment of textile dyeing wastewater is a major concern when effluent is directly discharged into the nearby environment. Long term disposal threatens the environment, which needs reclamation. This article reviews the current knowledge of nano zero valent iron (nZVI) technique in the degradation of textile dyes. The application of nZVI on textile dye degradation is receiving great attention in the recent years because nZVI particles are highly reactive towards the pollutant, less toxic, and economical. The nZVI particles aggregate quickly with respect to time and the addition of supports such as resin, nickel, zinc, bentonite, biopolymer, kaolin, rectorite, nickel-montmorillonite, bamboo, cellulose, biochar, graphene, and clinoptilolite enhanced the stability of iron nanoparticles. Inclusion of supports may in turn introduce additional toxic pollutants, hence green supports are recommended. The majority of investigations concluded dye color removal as textile dye compound removal, which is not factual. Very few studies monitored the removal of total organic carbon and observed the products formed. The results revealed that partial mineralization of the textile dye compound was achieved. Instead of stand alone technique, nZVI can be integrated with other suitable technique to achieve complete degradation of textile dye and also to treat multiple pollutants in the real textile dyeing wastewater. It is highly recommended to perform more bench-scale and pilot-scale studies to apply this technique to the textile effluent contaminated sites. Copyright © 2016 Elsevier Ltd. All rights reserved.

A New Synergetic Nanocomposite for Dye Degradation in Dark and Light

PubMed Central

V., Lakshmi Prasanna; Rajagopalan, Vijayaraghavan

2016-01-01

Environmental hazard caused due to the release of dyes in effluents is a concern in many countries. Among the various methods to combat this problem, Advanced Oxidation Process, in which semiconductor photocatalysts are used, is considered the most effective one. These materials release Reactive Oxygen Species (ROS) such as hydroxyl radical and superoxide in suspension that degrade the dyes into non-toxic minerals. However, this process requires visible or UV light for activation. Hence, there is a need to develop materials that release ROS, both in the absence and in the presence of light, so that the efficiency of dye removal is enhanced. Towards this objective, we have designed and synthesized a new nanocomposite ZnO2/polypyrrole which releases ROS even in the dark. The ROS released in the dark and in light were estimated by standard methods. It is to be noted that ZnO2 degrades the dye only under UV light but not in dark or in the presence of visible light. We propose the mechanism of dye degradation in dark and light. The synergically coupled nanocomposite of ZnO2/ppy is the first example that degrades dyes in the dark, through advanced oxidation process without employing additional reagents. PMID:27929084

The color removal of dye wastewater by magnesium chloride/red mud (MRM) from aqueous solution.

PubMed

Wang, Qi; Luan, Zhaokun; Wei, Ning; Li, Jin; Liu, Chengxi

2009-10-30

In this study, the MgCl2/red mud system (MRM) was used to investigate the color removal efficiency of dye solutions. Parameters such as the effect of the dosage of red mud (RM) and MgCl2 have been studied. The effect of pH on the conversion rate of Mg2+ has also been studied. The color removal efficiency of MRM was compared with that of PAC/RM and PAC/NaOH. Meanwhile, the color removal efficiency of RM was compared with that of NaOH. The results show that the MRM system can remove more than 98% of the coloring material at a dosage of 25 g RM/L dye solution and a volume of 1.5 mL MgCl2/L dye solution in the decolorization process of reactive dye, acid dye and direct dye. The color removal efficiency was better than PAC/RM and PAC/NaOH system. The adsorption data have been analyzed using Langmuir and Freundlich isotherms. The results indicated that both models provide the best correlation of the experimental data. The decolorization mechanism of MRM was discussed, too. The MRM system was a viable alternative to some of the more conventional forms of chemical treatment of dye solutions and also provided another way to make use of industrial waste red mud.

Photodegradation of environmental mutagens by visible irradiation in the presence of xanthene dyes as photosensitizers.

PubMed

Odo, Junichi; Torimoto, Sei-ichi; Nakanishi, Suguru; Niitani, Tomoya; Aoki, Hiroyuki; Inoguchi, Masahiko; Yamasaki, Yu

2012-01-01

The photodegradation of environmental mutagens, such as 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2), 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAαC), and 2-amino-3-methyl-imidazo[4,5-f]quinoline (IQ), was investigated by visible irradiation in the presence of xanthene dyes as photosensitizers. Although the environmental mutagens themselves were very stable during visible irradiation under the conditions in this study, they were effectively photodegraded in the presence of the xanthene dyes (erythrosine, rose bengal, and phloxine). Moreover, photodegradation of the mutagens was further enhanced for xanthene dyes loaded onto a water-soluble diethylaminoethyl (DEAE)-dextran anion-exchanger via ionic interactions (xanthene-dyeDEX). Photodegradation was inhibited by O2 removal from the reaction solution. In ESR spin-trapping experiments using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a trapping reagent, signals characteristic of DMPO-•OH (hydroxyl radical) were observed in the presence of xanthene-dyeDEX. These results suggest that reactive oxygen species derived from O2, such as singlet molecular oxygen (•1O2) and/or •OH, were active participants in photodegradation of the mutagens in the presence of xanthene dyes or xanthene-dyeDEX.

Dye surface coating enables visible light activation of TiO2 nanoparticles leading to degradation of neighboring biological structures.

PubMed

Blatnik, Jay; Luebke, Lanette; Simonet, Stephanie; Nelson, Megan; Price, Race; Leek, Rachael; Zeng, Leyong; Wu, Aiguo; Brown, Eric

2012-02-01

Biologically and chemically modified nanoparticles are gaining much attention as a new tool in cancer detection and treatment. Herein, we demonstrate that an alizarin red S (ARS) dye coating on TiO2 nanoparticles enables visible light activation of the nanoparticles leading to degradation of neighboring biological structures through localized production of reactive oxygen species. Successful coating of nanoparticles with dye is demonstrated through sedimentation, spectrophotometry, and gel electrophoresis techniques. Using gel electrophoresis, we demonstrate that visible light activation of dye-TiO2 nanoparticles leads to degradation of plasmid DNA in vitro. Alterations in integrity and distribution of nuclear membrane associated proteins were detected via fluorescence confocal microscopy in HeLa cells exposed to perinuclear localized ARS-TiO2 nanoparticles that were photoactivated with visible light. This study expands upon previous studies that indicated dye coatings on TiO2 nanoparticles can serve to enhance imaging, by clearly showing that dye coatings on TiO2 nanoparticles can also enhance the photoreactivity of TiO2 nanoparticles by allowing visible light activation. The findings of our study suggest a therapeutic application of dye-coated TiO2 nanoparticles in cancer research; however, at the same time they may reveal limitations on the use of dye assisted visualization of TiO2 nanoparticles in live-cell imaging.

Induction of fungal laccase production under solid state bioprocessing of new agroindustrial waste and its application on dye decolorization.

PubMed

Akpinar, Merve; Ozturk Urek, Raziye

2017-06-01

Lignocellulosic wastes are generally produced in huge amounts worldwide. Peach waste of these obtained from fruit juice industry was utilized as the substrate for laccase production by Pleurotus eryngii under solid state bioprocessing (SSB). Its chemical composition was determined and this bioprocess was carried out under stationary conditions at 28 °C. The effects of different compounds; copper, iron, Tween 80, ammonium nitrate and manganese, and their variable concentrations on laccase production were investigated in detail. The optimum production of laccase (43,761.33 ± 3845 U L -1 ) was achieved on the day of 20 by employing peach waste of 5.0 g and 70 µM Cu 2+ , 18 µM Fe 2+ , 0.025% (v/v) Tween 80, 4.0 g L -1 ammonium nitrate, 750 µM Mn 2+ as the inducers. The dye decolorization also researched to determine the degrading capability of laccase produced from peach culture under the above-mentioned conditions. Within this scope of the study, methyl orange, tartrazine, reactive red 2 and reactive black dyes were treated with this enzyme. The highest decolorization was performed with methyl orange as 43 ± 2.8% after 5 min of treatment when compared to other dyes. Up to now, this is the first report on the induction of laccase production by P. eryngii under SSB using peach waste as the substrate.

A dye-decolorizing peroxidase from Bacillus subtilis exhibiting substrate-dependent optimum temperature for dyes and β-ether lignin dimer

PubMed Central

Min, Kyoungseon; Gong, Gyeongtaek; Woo, Han Min; Kim, Yunje; Um, Youngsoon

2015-01-01

In the biorefinery using lignocellulosic biomass as feedstock, pretreatment to breakdown or loosen lignin is important step and various approaches have been conducted. For biological pretreatment, we screened Bacillus subtilis KCTC2023 as a potential lignin-degrading bacterium based on veratryl alcohol (VA) oxidation test and the putative heme-containing dye-decolorizing peroxidase was found in the genome of B. subtilis KCTC2023. The peroxidase from B. subtilis KCTC2023 (BsDyP) was capable of oxidizing various substrates and atypically exhibits substrate-dependent optimum temperature: 30°C for dyes (Reactive Blue19 and Reactive Black5) and 50°C for high redox potential substrates (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid [ABTS], VA, and veratryl glycerol-β-guaiacyl ether [VGE]) over +1.0 V vs. normal hydrogen electrode. At 50°C, optimum temperature for high redox potential substrates, BsDyP not only showed the highest VA oxidation activity (0.13 Umg−1) among the previously reported bacterial peroxidases but also successfully achieved VGE decomposition by cleaving Cα-Cβ bond in the absence of any oxidative mediator with a specific activity of 0.086 Umg−1 and a conversion rate of 53.5%. Based on our results, BsDyP was identified as the first bacterial peroxidase capable of oxidizing high redox potential lignin-related model compounds, especially VGE, revealing a previously unknown versatility of lignin degrading biocatalyst in nature. PMID:25650125

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goebel, Carsten, E-mail: goebel.c.1@pg.com; Troutman, John; Hennen, Jenny

The strong sensitizing potencies of the most important primary intermediates of oxidative hair dyes, p-phenylenediamine (PPD) and p-toluylenediamine (PTD, i.e. 2-methyl-PPD) are well established. They are considered as the key sensitizers in hair dye allergic contact dermatitis. While modification of their molecular structure is expected to alter their sensitizing properties, it may also impair their color performance. With introduction of a methoxymethyl side chain we found the primary intermediate 2-methoxymethyl-p-phenylenediamine (ME-PPD) with excellent hair coloring performance but significantly reduced sensitizing properties compared to PPD and PTD: In vitro, ME-PPD showed an attenuated innate immune response when analyzed for its proteinmore » reactivity and dendritic cell activation potential. In vivo, the effective concentration of ME-PPD necessary to induce an immune response 3-fold above vehicle control (EC3 value) in the local lymph node assay (LLNA) was 4.3%, indicating a moderate skin sensitizing potency compared to values of 0.1 and 0.17% for PPD and PTD, respectively. Finally, assessing the skin sensitizing potency of ME-PPD under consumer hair dye usage conditions through a quantitative risk assessment (QRA) indicated an allergy induction risk negligible compared to PPD or PTD. - Highlights: • Methoxymethyl side chain in p-phenylenediamine reduces its strong skin sensitizing properties. • Reduced protein reactivity and dendritic cell activation. • Reduced skin sensitizing potency in local lymph node assay (LLNA). • Negligible allergy induction risk under hair dye usage conditions.« less

New insight of hybrid membrane to degrade Congo red and Reactive yellow under sunlight.

PubMed

Rajeswari, A; Jackcina Stobel Christy, E; Pius, Anitha

2018-02-01

A study was carried out to investigate the degradation of organic contaminants (Congo red and Reactive yellow - 105) using cellulose acetate - polystyrene (CA-PS) membrane with and without ZnO impregnation. Scanning electron microscope (SEM), electron dispersive analysis of X-rays (EDAX), Fourier transform infrared spectrometer (FTIR), atomic force microscope (AFM) and thermogravimeric analysis (TG-DTA) analysis were carried out to characterize bare and ZnO impregnated CA-PS membranes. Membrane efficiency was also tested for pure water flux and antifouling performance. The modified membrane showed almost 85% water flux recovery. Blending of ZnO nanoparticles to CA-PS matrix could decrease membrane fouling and increase permeation quality of the membrane with above 90% of photocatalytic degradation efficiency for dyes. The rate of degradation of dyes was observed using UV-Vis spectrometer. Reusability of CA-PS-ZnO membrane was studied and no significant change was noted in the degradation efficiency until fourth cycle. Langmuir-Hinshelwood kinetic model well describes the photo degradation capacity and the degradation of dyes CR and RY - 105 exhibited pseudo-first order kinetics. The regression coefficient (R) of CR and RY - 105 found to be 0.99. The novelty of the prepared CA-PS-ZnO membrane is that it has better efficiency and high thermal stability than our previously reported material. Therefore, ZnO impregnated CA-PS membrane had proved to be an innovative alternative for the degradation of CR and RY - 105 dyes. Copyright © 2017 Elsevier B.V. All rights reserved.

Kinetics of ozone-initiated oxidation of textile dye, Amaranth in aqueous systems.

PubMed

Dachipally, Purnachandar; Jonnalagadda, Sreekanth B

2011-01-01

The ozone facilitated oxidation mechanism of water soluble azo anionic dye, amaranth (Am) was investigated monitoring the depletion kinetics of the dye spectrometrically at 521 nm. The oxidation kinetics of the dye by ozone was studied under semi-batch conditions, by bubbling ozone enriched oxygen through the aqueous reaction mixture of dye, as function of flow rate, ionic strength, [O(3)] and pH variations. With excess concentration of ozone and other reagents and low [amaranth], reaction followed pseudo-first-order kinetics with respect to the dye. Added neutral salts had marginal effect on the reaction rate and the variation of pH from 7 to 2 and 7 to 12 exerted only small increases in the reaction rate suggesting molecular ozone possibly is the principle reactive species in oxidation of dye. The reaction order with respect ozone was near unity and it varied slightly with pH and flow rate variations. The overall second-order rate constant for the reaction was (105 ± 4) M(-1) min(-1). The main oxidation products immediately after amaranth decolorization were identified. The reaction mechanism and overall rate law were proposed. After spiking the seawater, river water and wastewaters with Amaranth dye, the reaction rates and trends in BOD and COD under control and natural conditions were investigated. The rate of depletion of the dye in natural waters was relatively lower, but the ozonation process significantly decreased both the BOD and COD levels.

Bioremediation of the heavy metal complex dye Isolan Dark Blue 2SGL-01 by white rot fungus Irpex lacteus.

PubMed

Kalpana, Duraisamy; Shim, Jae Hong; Oh, Byung-Taek; Senthil, Kalaiselvi; Lee, Yang Soo

2011-12-30

The present study was conducted to evaluate the decolorization and degradation of the chromium metal complex dye Isolan Dark Blue 2SGL-01 by Irpex lacteus, a white rot lignolytic fungus. I. lacteus effectively decolorized the sulphonated reactive dye at a high concentration of 250 mg/l over a wide range of pH values of 5-9 and temperatures between 20 and 35°C. Complete (100%) decolorization occurred within 96h, and I. lacteus demonstrated resistance to the metallic dye. UV-vis spectroscopy, HPLC, GC-MS, and FT-IR analyses of the extracted metabolites confirmed that the decolorization process occurred due to degradation of the dye and not merely by adsorption. GC-MS analysis indicated the formation of 1(2H)-naphthalenone, 3,4-dihydro- and 2-naphthalenol as the main metabolite. ICP analysis demonstrated the removal of 13.49% chromium, and phytotoxicity studies using germinated seeds of Vigna radiata and Brassica juncea demonstrated the nontoxic nature of the metabolites formed during the degradation of Isolan Dark Blue 2SGL-01 dye. Copyright © 2011 Elsevier B.V. All rights reserved.

Preparation of Chitosan Coated Magnetic Hydroxyapatite Nanoparticles and Application for Adsorption of Reactive Blue 19 and Ni2+ Ions

PubMed Central

Nguyen, Van Cuong; Pho, Quoc Hue

2014-01-01

An adsorbent called chitosan coated magnetic hydroxyapatite nanoparticles (CS-MHAP) was prepared with the purpose of improvement for the removal of Ni2+ ions and textile dye by coprecipitation. Structure and properties of CS-MHAP were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and vibrating sample magnetometer (VSM). Weight percent of chitosan was investigated by thermal gravimetric analysis (TGA). The prepared CS-MHAP presents a significant improvement on the removal efficiency of Ni2+ ions and reactive blue 19 dye (RB19) in comparison with chitosan and magnetic hydroxyapatite nanoparticles. Moreover, the adsorption capacities were affected by several parameters such as contact time, initial concentration, adsorbent dosage, and initial pH. Interestingly, the prepared adsorbent could be easily recycled from an aqueous solution by an external magnet and reused for adsorption with high removal efficiency. PMID:24592158

Synthesis and characterization of photoswitchable fluorescent silica nanoparticles.

PubMed

Fölling, Jonas; Polyakova, Svetlana; Belov, Vladimir; van Blaaderen, Alfons; Bossi, Mariano L; Hell, Stefan W

2008-01-01

We have designed and synthesized a new functional (amino reactive) highly efficient fluorescent molecular switch (FMS) with a photochromic diarylethene and a rhodamine fluorescent dye. The reactive group in this FMS -N-hydroxysuccinimide ester- allows selective labeling of amino containing molecules or other materials. In ethanolic solutions, the compound displays a large fluorescent quantum yield of 52 % and a large fluorescence modulation ratio (94 %) between two states that may be interconverted with red and near-UV light. Silica nanoparticles incorporating the new FMS were prepared and characterized, and their spectroscopic and switching properties were also studied. The dye retained its properties after the incorporation into the silica, thereby allowing light-induced reversible high modulation of the fluorescence signal of a single particle for up to 60 cycles, before undergoing irreversible photobleaching. Some applications of these particles in fluorescence microscopy are also demonstrated. In particular, subdiffraction images of nanoparticles were obtained, in the focal plane of a confocal microscope.

Synthetic routes to 3(5)-phosphonylated pyrazoles

NASA Astrophysics Data System (ADS)

Goulioukina, N. S.; Makukhin, N. N.; Beletskaya, I. P.

2016-07-01

This review comprehensively covers the currently available synthetic routes to 3(5)-phosphonylated pyrazoles. There are demonstrated significant advances in this field over the last 10-15 years caused by the use of the Bestmann-Ohira reagent [as well as (diazomethyl)phosphonates and phosphonylated hydrazonoyl halides] in reactions with diverse dipolarophiles. 1,3-Dipolar cycloaddition of diazo compounds to α,β-unsaturated phosphonates as well as intramolecular heterocyclization of (1-diazoallyl)phosphonates and (3--diazo-1-propenyl)phosphonates are discussed. Synthetic potential of cyclocondensation of organophosphorus 1,3-dielectrophilic compounds with hydrazines is shown. Ways to introduce a phosphonate group into the pyrazole ring are considered. Examples of chemical transformations of 3(5)-phosphonylated pyrazoles are reported. The bibliography includes 88 references.

Structural dependence of the multi-functionalized carbon nanotubes to the substituents on the grafted diazo compounds

NASA Astrophysics Data System (ADS)

Amiri, Rahebeh; Rasouli, Sousan; Ghasemi, Alireza; Eghbali, Babak; Mohammadi, Soutodeh

2014-05-01

Systematic studies on the covalent functionalization of multi-walled carbon nanotubes were performed by a series of azo molecules with different substituents. For this investigation, 4-substituted diazonium reagents have been used in the reaction with the functionalized multi-walled carbon nanotubes. We analyzed the effect of the substituted groups on the diazo component affinity in the grafting. Also, the structural differences of the final products were evaluated by visual dispersion test, UV-Vis absorption. Fourier transforms infrared, Raman, and several complementary techniques (scanning electron microscopy, thermal gravimetric analysis, and colorimetry test). Nuclear magnetic resonance spectroscopy has been used to confirm the allylic protons attached to the surface of carbon nanotubes after functionalization.

Fluorescent silica nanoparticles containing covalently bound dyes for reporter, marker, and sensor applications

NASA Astrophysics Data System (ADS)

Patonay, Gabor; Henary, Maged; Chapman, Gala; Emer, Kyle; Crow, Sidney

2016-03-01

Silica nanoparticles have proven to be useful in many bioanalytical and medical applications and have been used in numerous applications during the last decade. Combining the properties of silica nanoparticles and fluorescent dyes that may be used as chemical probes or labels can be relatively easy by simply soaking porous silica nanoparticles in a solution of the dye of interest. Under proper conditions the entrapped dye can stay inside the silica nanoparticle for several hours resulting in a useful probe. In spite of the relative durability of these probes, leaching can still occur. A much better approach is to synthesize silica nanoparticles that have the fluorescent dye covalently attached to the backbone structure of the silica nanoparticle. This can be achieved by using appropriately modified tetraethyl orthosilicate (TEOS) analogues during the silica nanoparticle synthesis. The molar ratio of TEOS and modified TEOS will determine the fluorescent dye load in the silica nanoparticle. Dependent on the chemical stability of the reporting dye either reverse micellar (RM) or Stöber method can be used for silica nanoparticle synthesis. If dye stability allows RM procedure is preferred as it results in a much easier control of the silica nanoparticle reaction itself. Also controlling the size and uniformity of the silica nanoparticles are much easier using RM method. Dependent on the functional groups present in the reporting dye used in preparation of the modified TEOS, the silica nanoparticles can be utilized in many applications such as pH sensor, metal ion sensors, labels, etc. In addition surface activated silica nanoparticles with reactive moieties are also excellent reporters or they can be used as bright fluorescent labels. Many different fluorescent dyes can be used to synthesize silica nanoparticles including visible and NIR dyes. Several bioanalytical applications are discussed including studying amoeba phagocytosis.

Decolourization of dye-containing effluent using mineral coagulants produced by electrocoagulation.

PubMed

Zidane, Fatiha; Drogui, Patrick; Lekhlif, Brahim; Bensaid, Jalila; Blais, Jean-François; Belcadi, Said; El Kacemi, Kacem

2008-06-30

The colour and colour causing-compounds has always been undesirable in water for any use, be it industrial or domestic wastewaters. The discharge of such effluents causes excessive oxygen demand in the receiving water and then a treatment is required before discharge into ecosystems. This study examined the possibility to remove colour causing-compounds from effluent by chemical coagulation, in comparison with direct electrocoagulation. The inorganic coagulants (C1, C2 and C3) in the form of dry powder tested, were respectively produced from electrolysis of S1=[NaOH (7.5 x 10(-3)M)], S2=[NaCl (10(-2)M)], and S3=[NaOH (7.5 x 10(-3)M)+NaCl (10(-2)M)] solutions, using sacrificial aluminium electrodes operated at an electrical potential of 12 V. Reactive textile dye (CI Reactive Red 141) was used as model of colour-causing compound prepared at a concentration of 50 mgl(-1). The best performances of dye removal were obtained with C(2) having a chemical structure comprised of a mixture of polymeric specie (Al45O45(OH)45Cl) and monomeric species (AlCl(OH)2.2H2O and Al(OH)3). The removal efficiency (R(A)) evaluated by measuring the yields of 540 nm-absorbance removal varied from 41 to 96% through 60 min of treatment by imposing a concentration of C2 ranging from 100 to 400 mg l(-1). The effectiveness of the treatment increased and the effluent became more and more transparent while increasing C(2) concentration. The comparison of chemical treatment using C2 coagulant and direct electrocoagulation of CI Reactive Red 141 containing synthetic solution demonstrated the advantage of chemical treatment during the first few minutes of treatment. A yield of 88% of absorbance removal was recorded using C2 coagulant (400 mg l(-1)) over the first 10 min of treatment, compared to 60% measured using direct electrocoagulation while imposing either 10 or 15 V of electrical potential close to the value (12 V) required during C2 production. However, at the end of the treatment (after 60 min of treatment), CI Reactive Red 141 pollutant was completely removed from solution (540 nm-absorbance removal of 100%) using direct electrochemical treatment, compared to 96.4% of absorbance removed while treating dye-containing synthetic solution by means of C2 coagulant.

Fly ash-TiO2 nanocomposite material for multi-pollutants wastewater treatment.

PubMed

Visa, Maria; Andronic, Luminita; Duta, Anca

2015-03-01

This paper reports on the synthesis, characterization and adsorption properties of a novel nano-composite obtained using the hydrothermal method applied to a fly ash-TiO2 slurry and hexadecyltrimethyl-ammonium bromide, as surface controlling agent. The new adsorbent was investigated in terms of crystallinity (XRD), surface properties (AFM, SEM, and porosity and BET surface) and surface chemistry (EDX, FTIR). The nanocomposite's properties were sequentially tested in adsorption and photocatalysis processes applied to multi-pollutant synthetic wastewaters loaded with copper cations and two industrial dyes: the acid dye Bemacid Blau and the reactive dye Bemacid Rot; the nano-composite substrate allowed reaching high removal efficiencies, above 90%, both in adsorption and in photodegradation experiments, in optimised conditions. Copyright © 2014. Published by Elsevier Ltd.

Detection of gain enhancement in laser-induced fluorescence of rhodamine B lasing dye by silicon dioxide nanostructures-coated cavity

NASA Astrophysics Data System (ADS)

Al-Tameemi, Mohammed N. A.

2018-03-01

In this work, nanostructured silicon dioxide films are deposited by closed-field unbalanced direct-current (DC) reactive magnetron sputtering technique on two sides of quartz cells containing rhodamine B dye dissolved in ethanol with 10‒5 M concentration as a random gain medium. The preparation conditions are optimized to prepare highly pure SiO2 nanostructures with a minimum particle size of about 20 nm. The effect of SiO2 films as external cavity for the random gain medium is determined by the laser-induced fluorescence of this medium, and an increase of about 200% in intensity is observed after the deposition of nanostructured SiO2 thin films on two sides of the dye cell.

Rh(V) -Nitrenoid as a Key Intermediate in Rh(III) -Catalyzed Heterocyclization by C-H Activation: A Computational Perspective on the Cycloaddition of Benzamide and Diazo Compounds.

PubMed

Zhou, Tao; Guo, Wei; Xia, Yuanzhi

2015-06-15

A mechanistic study of the substituent-dependent ring formations in Rh(III) -catalyzed C-H activation/cycloaddition of benzamide and diazo compounds was carried out by using DFT calculations. The results indicated that the decomposition of the diazo is facilitated upon the formation of the five-membered rhodacycle, in which the Rh(III) center is more electrophilic. The insertion of carbenoid into Rh-C(phenyl) bond occurs readily and forms a 6-membered rhodacycle, however, the following C-N bond formation is difficult both kinetically and thermodynamically by reductive elimination from the Rh(III) species. Instead, the Rh(V) -nitrenoid intermediate could be formed by migration of the pivalate from N to Rh, which undergoes the heterocyclization much more easily and complementary ring-formations could be modulated by the nature of the substituent at the α-carbon. When a vinyl is attached, the stepwise 1,3-allylic migration occurs prior to the pivalate migration and the 8-membered ring product will be formed. On the other hand, the pivalate migration becomes more favorable for the phenyl-contained intermediate because of the difficult 1,3-allylic migration accompanied by dearomatization, thus the 5-membered ring product was formed selectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal structure of 5-{4'-[(2-{2-[2-(2-ammonio-eth-oxy)eth-oxy]eth-oxy}eth-yl)carbamo-yl]-4-meth-oxy-[1,1'-biphen-yl]-3-yl}-3-oxo-1,2,5-thia-diazo-lidin-2-ide 1,1-dioxide: a potential inhibitor of the enzyme protein tyrosine phosphatase 1B (PTP1B).

PubMed

Ruddraraju, Kasi Viswanatharaju; Hillebrand, Roman; Barnes, Charles L; Gates, Kent S

2015-04-01

The title compound, C24H32N4O8S, (I), crystallizes as a zwitterion. The terminal amine N atom of the [(2-{2-[2-(2-ammonio-eth-oxy)eth-oxy]eth-oxy}eth-yl)carbamo-yl] side chain is protonated, while the 1,2,5-thia-diazo-lidin-3-one 1,1-dioxide N atom is deprotonated. The side chain is turned over on itself with an intra-molecular N-H⋯O hydrogen bond. The 1,2,5-thia-diazo-lidin-3-one 1,1-dioxide ring has an envelope conformation with the aryl-substituted N atom as the flap. Its mean plane is inclined by 62.87 (8)° to the aryl ring to which it is attached, while the aryl rings of the biphenyl unit are inclined to one another by 20.81 (8)°. In the crystal, mol-ecules are linked by N-H⋯O and N-H⋯N hydrogen bonds, forming slabs lying parallel to (010). Within the slabs there are C-H⋯O and C-H⋯N hydrogen bonds and C-H⋯π inter-actions present.

Patch testing to a textile dye mix by the international contact dermatitis research group.

PubMed

Isaksson, Marléne; Ale, Iris; Andersen, Klaus E; Diepgen, Thomas; Goh, Chee-Leok; Goossens R, An; Jerajani, Hemangi; Maibach, Howard I; Sasseville, Denis; Bruze, Magnus

2015-01-01

Disperse dyes are well-known contact sensitizers not included in the majority of commercially available baseline series. To investigate the outcome of patch testing to a textile dye mix (TDM) consisting of 8 disperse dyes. Two thousand four hundred ninety-three consecutive dermatitis patients in 9 dermatology clinics were patch tested with a TDM 6.6%, consisting of Disperse (D) Blue 35, D Yellow 3, D Orange 1 and 3, D Red 1 and 17, all 1.0% each, and D Blue 106 and D Blue 124, each 0.3%. 90 reacted positively to the TDM. About 92.2% of the patients allergic to the TDM were also tested with the 8 separate dyes. Contact allergy to TDM was found in 3.6% (1.3-18.2) Simultaneous reactivity to p-phenylenediamine was found in 61.1% of the TDM-positive patients. Contact allergy to TDM and not to other p-amino-substituted sensitizers was diagnosed in 1.2%. The most frequent dye allergen in the TDM-positive patients was D Orange 3. Over 30% of the TDM allergic patients had been missed if only the international baseline series was tested. Contact allergy to TDM could explain or contribute to dermatitis in over 20% of the patients. Textile dye mix should be considered for inclusion into the international baseline series.

Comparative study on the process behavior and reaction kinetics in sonocatalytic degradation of organic dyes by powder and nanotubes TiO2.

PubMed

Pang, Yean Ling; Abdullah, Ahmad Zuhairi

2012-05-01

Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO(2) was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO(2) was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO(2) nanotubes could be up to four times as compared to TiO(2) powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO(2) nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO(2) nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO(2) nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO(2) nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes. Copyright © 2011 Elsevier B.V. All rights reserved.

Degradation of organic dyes using spray deposited nanocrystalline stratified WO3/TiO2 photoelectrodes under sunlight illumination

NASA Astrophysics Data System (ADS)

Hunge, Y. M.; Yadav, A. A.; Mahadik, M. A.; Bulakhe, R. N.; Shim, J. J.; Mathe, V. L.; Bhosale, C. H.

2018-02-01

The need to utilize TiO2 based metal oxide hetero nanostructures for the degradation of environmental pollutants like Rhodamine B and reactive red 152 from the wastewater using stratified WO3/TiO2 catalyst under sunlight illumination. WO3, TiO2 and stratified WO3/TiO2 catalysts were prepared by a spray pyrolysis method. It was found that the stratified WO3/TiO2 heterostructure has high crystallinity, no mixed phase formation occurs, strong optical absorption in the visible region of the solar spectrum, and large surface area. The photocatalytic activity was tested for degradation of Rhodamine B (Rh B) and reactive red 152 in an aqueous medium. TiO2 layer in stratified WO3/TiO2 catalyst helps to extend its absorption spectrum in the solar light region. Rh B and Reactive red 152is eliminated up to 98 and 94% within the 30 and 40 min respectively at optimum experimental condition by stratified WO3/TiO2. Moreover, stratified WO3/TiO2 photoelectrode has good stability and reusability than individual TiO2 and WO3 thin film in the degradation of Rh B and reactive red 152. The photoelectrocatalytic experimental results indicate that stratified WO3/TiO2 photoelectrode is a promising material for dye removal.

Marine green algae Codium iyengarii as a good bio-sorbent for elimination of reactive black 5 from aqueous solution.

PubMed

Azmat, Rafia

2014-09-01

The green seaweeds Codium iyengarii (C. iyengarii) was used to prepare as an adsorbent surface for the deletion of Reactive Black 5 (RB 5) from aqueous solution via adsorption. The batch technique was adopted under the optimal condition of amount of adsorbent, agitation time, concentration of dye, and at neutral and low pH. The depletion in concentration of the dye was monitored by Schimadzo 180 AUV/Visible spectrophotometer. It was initially monolayer adsorption, which showed multilayered formation later on with the passage of time at low and neutral pH. The Results displayed that adsorptive ability of C. iyengarii was 1.95-3.82mg/g with an elevation in primary application of dye contents (50ppm-70 ppm). The elimination data were well stable into the Langmuir and Freundlich adsorption isotherm equations. The Langmuir (R2=0.9848) and Freundlich (R2=0.9441) constants for biosorption of RB 5 on green algae were determined. The coefficient relation values suggested that the Langmuir isotherm was well fitted. It explained the interaction of surface molecules, which helps in well organization of dye molecules in a monolayer formation initially on algal biomass. The pseudo first and second order rate equations were applied to link the investigational statistics and found that the second order rate expression was found to be more suitable for both the models. The absorption spectrum of RB 5 before and after adsorption with respect to time was monitored which clearly indicate that C. iyengarii was much effective surface at very low quantity.

Visible light-induced photocatalytic degradation of Reactive Blue-19 over highly efficient polyaniline-TiO2 nanocomposite: a comparative study with solar and UV photocatalysis.

PubMed

Kalikeri, Shankramma; Kamath, Nidhi; Gadgil, Dhanashri Jayant; Shetty Kodialbail, Vidya

2018-02-01

Polyaniline-TiO 2 (PANI-TiO 2 ) nanocomposite was prepared by in situ polymerisation method. X-ray diffractogram (XRD) showed the formation of PANI-TiO 2 nanocomposite with the average crystallite size of 46 nm containing anatase TiO 2 . The PANI-TiO 2 nanocomposite consisted of short-chained fibrous structure of PANI with spherical TiO 2 nanoparticles dispersed at the tips and edge of the fibres. The average hydrodynamic diameter of the nanocomposite was 99.5 nm. The band gap energy was 2.1 eV which showed its ability to absorb light in the visible range. The nanocomposite exhibited better visible light-mediated photocatalytic activity than TiO 2 (Degussa P25) in terms of degradation of Reactive Blue (RB-19) dye. The photocatalysis was favoured under initial acidic pH, and complete degradation of 50 mg/L dye could be achieved at optimum catalyst loading of 1 g/L. The kinetics of degradation followed the Langmuir-Hinshelhood model. PANI-TiO 2 nanocomposite showed almost similar photocatalytic activity under UV and visible light as well as in the solar light which comprises of radiation in both UV and visible light range. Chemical oxygen demand removal of 86% could also be achieved under visible light, confirming that simultaneous mineralization of the dye occurred during photocatalysis. PANI-TiO 2 nanocomposites are promising photocatalysts for the treatment of industrial wastewater containing RB-19 dye.

A comparison of antibacterial and antibiofilm efficacy of phenothiazinium dyes between Gram positive and Gram negative bacterial biofilm.

PubMed

Misba, Lama; Zaidi, Sahar; Khan, Asad U

2017-06-01

Antimicrobial photodynamic therapy (APDT) is a process that generates reactive oxygen species (ROS) in presence of photosensitizer, visible light and oxygen which destroys the bacterial cells. We investigated the photoinactivation efficiency of phenothiazinium dyes and the effect of ROS generation on Gram positive and Gram negative bacterial cell as well as on biofilm. Enterococcus faecalis and Klebsiella pneumonia were incubated with all the three phenothiazinium dyes and exposed to 630nm of light. After PDT, colony forming unit (CFU) were performed to estimate the cell survival fraction. Intracellular reactive oxygen species (ROS) was detected by DCFH-DA. Crystal violet (CV) assay and extracellular polysaccharides (EPS) reduction assay were performed to analyze antibiofilm effect. Confocal laser electron microscope (CLSM) scanning electron microscope (SEM) was performed to assess the disruption of biofilm. 8log 10 reduction in bacterial count was observed in Enterococcus faecalis while 3log 10 in Klebsiella pneumoniae. CV and EPS reduction assay revealed that photodynamic inhibition was more pronounced in Enterococcus faecalis. In addition to this CLSM and SEM study showed an increase in cell permeability of propidium iodide and leakage of cellular constituents in treated preformed biofilm which reflects the antibiofilm action of photodynamic therapy. We conclude that Gram-positive bacteria (Enterococcus faecalis) are more susceptible to APDT due to increased level of ROS generation inside the cell, higher photosensitizer binding efficiency and DNA degradation. Phenothiazinium dyes are proved to be highly efficient against both planktonic and biofilm state of cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Bifunctional Diaminoterephthalate Fluorescent Dye as Probe for Cross-Linking Proteins.

PubMed

Wallisch, Melanie; Sulmann, Stefan; Koch, Karl-Wilhelm; Christoffers, Jens

2017-05-11

Diaminoterephthalates are fluorescent dyes and define scaffolds, which can be orthogonally functionalized at their two carboxylate residues with functional residues bearing task specific reactive groups. The synthesis of monofunctionalized dyes with thiol groups for surface binding, an azide for click chemistry, and a biotinoylated congener for streptavidin binding is reported. Two bifunctionalized dyes were prepared: One with an azide for click chemistry and a biotin for streptavidin binding, the other with a maleimide for reaction with thiol and a cyclooctyne moiety for ligation with copper-free click chemistry. In general, the compounds are red to orange, fluorescent materials with an absorption at about 450 nm and an emission at 560 nm with quantum yields between 2-41 %. Of particular interest is the maleimide-functionalized compound, which shows low fluorescence quantum yield (2 %) by itself. After addition of a thiol, the fluorescence is "turned on"; quantum yield 41 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of an activated carbon-packed microbial bioelectrochemical system for azo dye degradation.

PubMed

Cardenas-Robles, Arely; Martinez, Eduardo; Rendon-Alcantar, Idelfonso; Frontana, Carlos; Gonzalez-Gutierrez, Linda

2013-01-01

A microbial bioelectrochemical reactor (BER) was employed for the degradation of azo dyes without the use of an external electron donor, using activated carbon (GAC) as a redox mediator. Contribution of pH values, open circuit potential (OCP), dye concentration and applied current were individually studied. A batch system and an upflow fixed bed bioreactor were built for analyzing the effect of the applied current on biodegradation of the azo dye Reactive Red 272. The presence of GAC (20% w/v) regulated both pH and OCP values in solution and led to a removal efficiency of 98%. Cyclic voltammetry results indicate a dependence of the electron transfer mechanism with the concentration of the azo compound. With these results, a continuous flow reactor operating with J=0.045 mA cm(-2), led to removal rates of 95% (± 3.5%) in a half-residence time of 1 hour. Copyright © 2012 Elsevier Ltd. All rights reserved.

Decolorization of the anthraquinone dye Cibacron Blue 3G-A with immobilized Coprinus cinereus in fluidized bed bioreactor.

PubMed

Moutaouakkil, A; Blaghen, M

2011-01-01

Coprinus cinereus, which was able to decolorize the anthraquinone dye Cibacron Blue 3G-A (CB) enzymatically, was used as a biocatalyst for the decolorization of synthetic solutions containing this reactive dye. Coprinus cinereus was immobilized in both calcium alginate and polyacrylamide gels, and was used for the decolorization of CB from synthetic water by using a fluidized bed bioreactor. The highest specific decolorization rate was obtained when Coprinus cinereus was entrapped in calcium alginate beads, and was of about 3.84 mg g(-1) h(-1) with a 50% conversion time (t1/2) of about 2.60 h. Moreover, immobilized fungal biomass in calcium alginate continuously decolorized CB even after 7 repeated experiments without significant loss of activity, while polyacrylamide-immobilized fungal biomass retained only 67% of its original activity. The effects of some physicochemical parameters such as temperature, pH and dye concentration on decolorization performance of isolated fungal strain were also investigated.

Mechanism and comparison of needle-type non-thermal direct and indirect atmospheric pressure plasma jets on the degradation of dyes

NASA Astrophysics Data System (ADS)

Attri, Pankaj; Yusupov, Maksudbek; Park, Ji Hoon; Lingamdinne, Lakshmi Prasanna; Koduru, Janardhan Reddy; Shiratani, Masaharu; Choi, Eun Ha; Bogaerts, Annemie

2016-10-01

Purified water supply for human use, agriculture and industry is the major global priority nowadays. The advanced oxidation process based on atmospheric pressure non-thermal plasma (NTP) has been used for purification of wastewater, although the underlying mechanisms of degradation of organic pollutants are still unknown. In this study we employ two needle-type atmospheric pressure non-thermal plasma jets, i.e., indirect (ID-APPJ) and direct (D-APPJ) jets operating at Ar feed gas, for the treatment of methylene blue, methyl orange and congo red dyes, for two different times (i.e., 20 min and 30 min). Specifically, we study the decolorization/degradation of all three dyes using the above mentioned plasma sources, by means of UV-Vis spectroscopy, HPLC and a density meter. We also employ mass spectroscopy to verify whether only decolorization or also degradation takes place after treatment of the dyes by the NTP jets. Additionally, we analyze the interaction of OH radicals with all three dyes using reactive molecular dynamics simulations, based on the density functional-tight binding method. This investigation represents the first report on the degradation of these three different dyes by two types of NTP setups, analyzed by various methods, and based on both experimental and computational studies.

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films.

PubMed

Moia, Davide; Szumska, Anna; Vaissier, Valérie; Planells, Miquel; Robertson, Neil; O'Regan, Brian C; Nelson, Jenny; Barnes, Piers R F

2016-10-12

Charge recombination between oxidized dyes attached to mesoporous TiO 2 and electrons in the TiO 2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO 2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts.

Bio-remediation of colored industrial wastewaters by the white-rot fungi Phanerochaete chrysosporium and Pleurotus ostreatus and their enzymes.

PubMed

Faraco, V; Pezzella, C; Miele, A; Giardina, P; Sannia, G

2009-04-01

The effect of Phanerochaete chrysosporium and Pleurotus ostreatus whole cells and their ligninolytic enzymes on models of colored industrial wastewaters was evaluated. Models of acid, direct and reactive dye wastewaters from textile industry have been defined on the basis of discharged amounts, economic relevance and representativeness of chemical structures of the contained dyes. Phanerochaete chrysosporium provided an effective decolourization of direct dye wastewater model, reaching about 45% decolourization in only 1 day of treatment, and about 90% decolourization within 7 days, whilst P. ostreatus was able to decolorize and detoxify acid dye wastewater model providing 40% decolourization in only 1 day, and 60% in 7 days. P. ostreatus growth conditions that induce laccase production (up to 130,000 U/l) were identified, and extra-cellular enzyme mixtures, with known laccase isoenzyme composition, were produced and used in wastewater models decolourization. The mixtures decolorized and detoxified the acid dye wastewater model, suggesting laccases as the main agents of wastewater decolourization by P. ostreatus. A laccase mixture was immobilized by entrapment in Cu-alginate beads, and the immobilized enzymes were shown to be effective in batch decolourization, even after 15 stepwise additions of dye for a total exposure of about 1 month.

Fractional Factorial Design Study on the Performance of GAC-Enhanced Electrocoagulation Process Involved in Color Removal from Dye Solutions.

PubMed

Secula, Marius Sebastian; Cretescu, Igor; Cagnon, Benoit; Manea, Liliana Rozemarie; Stan, Corneliu Sergiu; Breaban, Iuliana Gabriela

2013-07-10

The aim of this study was to determine the effects of main factors and interactions on the color removal performance from dye solutions using the electrocoagulation process enhanced by adsorption on Granular Activated Carbon (GAC). In this study, a mathematical approach was conducted using a two-level fractional factorial design ( FFD ) for a given dye solution. Three textile dyes: Acid Blue 74, Basic Red 1, and Reactive Black 5 were used. Experimental factors used and their respective levels were: current density (2.73 or 27.32 A/m²), initial pH of aqueous dye solution (3 or 9), electrocoagulation time (20 or 180 min), GAC dose (0.1 or 0.5 g/L), support electrolyte (2 or 50 mM), initial dye concentration (0.05 or 0.25 g/L) and current type (Direct Current- DC or Alternative Pulsed Current- APC ). GAC-enhanced electrocoagulation performance was analyzed statistically in terms of removal efficiency, electrical energy, and electrode material consumptions, using modeling polynomial equations. The statistical significance of GAC dose level on the performance of GAC enhanced electrocoagulation and the experimental conditions that favor the process operation of electrocoagulation in APC regime were determined. The local optimal experimental conditions were established using a multi-objective desirability function method.

Hydrogen production and metal-dye bioremoval by a Nostoc linckia strain isolated from textile mill oxidation pond.

PubMed

Mona, Sharma; Kaushik, Anubha; Kaushik, C P

2011-02-01

Biohydrogen production by Nostoc linckia HA-46, isolated from a textile-industry oxidation-pond was studied by varying light/dark period, pH, temperature and ratio of carbon-dioxide and argon in the gas-mixture. Hydrogen production rates were maximum under 18 h of light and 6 h of darkness, pH 8.0, 31°C, a CO(2):Ar ratio 2:10. Hydrogen production of the strain acclimatized to 20 mg/L of chromium/cobalt and 100 mg/L of Reactive red 198/crystal violet dye studied in N-supplemented/deficient medium was 6-10% higher in the presence of 1.5 g/L of NaNO(3). Rates of hydrogen production in the presence of dyes/metals by the strain (93-105 μmol/h/mg Chlorophyll) were significantly higher than in medium without metals/dyes serving as control (91.3 μmol/h/mg Chlorophyll). About 58-60% of the two metals and 35-73% of dyes were removed by cyanobacterium. Optimal conditions of temperature, pH and metals/dyes concentration for achieving high hydrogen production and wastewater treatment were found practically applicable as similar conditions are found in the effluent of regional textile-mills. Copyright © 2010 Elsevier Ltd. All rights reserved.

Fractional Factorial Design Study on the Performance of GAC-Enhanced Electrocoagulation Process Involved in Color Removal from Dye Solutions

PubMed Central

Secula, Marius Sebastian; Cretescu, Igor; Cagnon, Benoit; Manea, Liliana Rozemarie; Stan, Corneliu Sergiu; Breaban, Iuliana Gabriela

2013-01-01

The aim of this study was to determine the effects of main factors and interactions on the color removal performance from dye solutions using the electrocoagulation process enhanced by adsorption on Granular Activated Carbon (GAC). In this study, a mathematical approach was conducted using a two-level fractional factorial design (FFD) for a given dye solution. Three textile dyes: Acid Blue 74, Basic Red 1, and Reactive Black 5 were used. Experimental factors used and their respective levels were: current density (2.73 or 27.32 A/m2), initial pH of aqueous dye solution (3 or 9), electrocoagulation time (20 or 180 min), GAC dose (0.1 or 0.5 g/L), support electrolyte (2 or 50 mM), initial dye concentration (0.05 or 0.25 g/L) and current type (Direct Current—DC or Alternative Pulsed Current—APC). GAC-enhanced electrocoagulation performance was analyzed statistically in terms of removal efficiency, electrical energy, and electrode material consumptions, using modeling polynomial equations. The statistical significance of GAC dose level on the performance of GAC enhanced electrocoagulation and the experimental conditions that favor the process operation of electrocoagulation in APC regime were determined. The local optimal experimental conditions were established using a multi-objective desirability function method. PMID:28811405

Petrophilic, Fe(III) Reducing Exoelectrogen Citrobacter sp. KVM11, Isolated From Hydrocarbon Fed Microbial Electrochemical Remediation Systems

PubMed Central

Venkidusamy, Krishnaveni; Hari, Ananda Rao; Megharaj, Mallavarapu

2018-01-01

Exoelectrogenic biofilms capable of extracellular electron transfer are important in advanced technologies such as those used in microbial electrochemical remediation systems (MERS) Few bacterial strains have been, nevertheless, obtained from MERS exoelectrogenic biofilms and characterized for bioremediation potential. Here we report the identification of one such bacterial strain, Citrobacter sp. KVM11, a petrophilic, iron reducing bacterial strain isolated from hydrocarbon fed MERS, producing anodic currents in microbial electrochemical systems. Fe(III) reduction of 90.01 ± 0.43% was observed during 5 weeks of incubation with Fe(III) supplemented liquid cultures. Biodegradation screening assays showed that the hydrocarbon degradation had been carried out by metabolically active cells accompanied by growth. The characteristic feature of diazo dye decolorization was used as a simple criterion for evaluating the electrochemical activity in the candidate microbe. The electrochemical activities of the strain KVM11 were characterized in a single chamber fuel cell and three electrode electrochemical cells. The inoculation of strain KVM11 amended with acetate and citrate as the sole carbon and energy sources has resulted in an increase in anodic currents (maximum current density) of 212 ± 3 and 359 ± mA/m2 with respective coulombic efficiencies of 19.5 and 34.9% in a single chamber fuel cells. Cyclic voltammetry studies showed that anaerobically grown cells of strain KVM11 are electrochemically active whereas aerobically grown cells lacked the electrochemical activity. Electrobioremediation potential of the strain KVM11 was investigated in hydrocarbonoclastic and dye detoxification conditions using MERS. About 89.60% of 400 mg l-1 azo dye was removed during the first 24 h of operation and it reached below detection limits by the end of the batch operation (60 h). Current generation and biodegradation capabilities of strain KVM11 were examined using an initial concentration of 800 mg l-1 of diesel range hydrocarbons (C9-C36) in MERS (maximum currentdensity 50.64 ± 7 mA/m2; power density 4.08 ± 2 mW/m2, 1000 ω, hydrocarbon removal 60.14 ± 0.7%). Such observations reveal the potential of electroactive biofilms in the simultaneous remediation of hydrocarbon contaminated environments with generation of energy. PMID:29593662

Petrophilic, Fe(III) Reducing Exoelectrogen Citrobacter sp. KVM11, Isolated From Hydrocarbon Fed Microbial Electrochemical Remediation Systems.

PubMed

Venkidusamy, Krishnaveni; Hari, Ananda Rao; Megharaj, Mallavarapu

2018-01-01

Exoelectrogenic biofilms capable of extracellular electron transfer are important in advanced technologies such as those used in microbial electrochemical remediation systems (MERS) Few bacterial strains have been, nevertheless, obtained from MERS exoelectrogenic biofilms and characterized for bioremediation potential. Here we report the identification of one such bacterial strain, Citrobacter sp. KVM11, a petrophilic, iron reducing bacterial strain isolated from hydrocarbon fed MERS, producing anodic currents in microbial electrochemical systems. Fe(III) reduction of 90.01 ± 0.43% was observed during 5 weeks of incubation with Fe(III) supplemented liquid cultures. Biodegradation screening assays showed that the hydrocarbon degradation had been carried out by metabolically active cells accompanied by growth. The characteristic feature of diazo dye decolorization was used as a simple criterion for evaluating the electrochemical activity in the candidate microbe. The electrochemical activities of the strain KVM11 were characterized in a single chamber fuel cell and three electrode electrochemical cells. The inoculation of strain KVM11 amended with acetate and citrate as the sole carbon and energy sources has resulted in an increase in anodic currents (maximum current density) of 212 ± 3 and 359 ± mA/m 2 with respective coulombic efficiencies of 19.5 and 34.9% in a single chamber fuel cells. Cyclic voltammetry studies showed that anaerobically grown cells of strain KVM11 are electrochemically active whereas aerobically grown cells lacked the electrochemical activity. Electrobioremediation potential of the strain KVM11 was investigated in hydrocarbonoclastic and dye detoxification conditions using MERS. About 89.60% of 400 mg l -1 azo dye was removed during the first 24 h of operation and it reached below detection limits by the end of the batch operation (60 h). Current generation and biodegradation capabilities of strain KVM11 were examined using an initial concentration of 800 mg l -1 of diesel range hydrocarbons (C9-C36) in MERS (maximum currentdensity 50.64 ± 7 mA/m 2 ; power density 4.08 ± 2 mW/m 2 , 1000 ω, hydrocarbon removal 60.14 ± 0.7%). Such observations reveal the potential of electroactive biofilms in the simultaneous remediation of hydrocarbon contaminated environments with generation of energy.

Pivotal role of glutathione depletion in plasma-induced endothelial oxidative stress during sepsis.

PubMed

Huet, Olivier; Cherreau, Christaine; Nicco, Carole; Dupic, Laurent; Conti, Marc; Borderie, Didier; Pene, Frédéric; Vicaut, Eric; Benhamou, Dan; Mira, Jean-Paul; Duranteau, Jacques; Batteux, Frédéric

2008-08-01

Plasma from septic shock patients can induce production of reactive oxygen species (ROS) by human umbilical vein endothelial cells (HUVEC) in vitro. How endothelial cells defend themselves against ROS under increased oxidative stress has not yet been examined. This study investigates the antioxidant defenses of HUVEC exposed to plasma obtained from either septic shock patients or healthy volunteers. Prospective, observational study. Medical intensive care unit in a university hospital. Twenty-five patients with septic shock and 10 healthy volunteers. Blood samples were collected within the first 24 hrs of septic shock. In vitro HUVEC production of ROS was studied by spectrofluorimetry using 2',7'-dichlorodihydrofluorescein diacetate fluorescent dye. Reactive nitrogen species were also assessed. Intracellular reduced glutathione (GSH) levels were measured using monochlorobimane fluorescent dye. Activity of catalase and superoxide dismutase in HUVEC were also measured. Cell death was assessed using YOPRO fluorescent dye and the MTT assay. On admission, the septic shock population's mean age was 55 yrs old, the mean Sequential Organ Failure Assessment score was 12, mean simplified acute physiology score was 50, and intensive care unit mortality rate was 45%. Evaluation of HUVEC antioxidant defenses showed a significantly decreased GSH level, increased catalase activity, and unchanged superoxide dismutase activity. ROS levels and cell death were significantly reduced when cells were pretreated with N-acetylcysteine or GSH, but no changes in reactive nitrogen species were observed. This study demonstrates that plasma-induced ROS production by HUVEC is associated with an intracellular decrease in reduced GSH. Both ROS levels and cell death decreased when N-acetylcysteine or GSH were added before exposing the cells to plasma. These data suggest a pivotal role of alterations in GSH in damage caused by sepsis-generated ROS in endothelial cell.

Synthesis, characterization, and application of cy-dye- and alexa-dye-labeled hongotoxin(1) analogues. The first high affinity fluorescence probes for voltage-gated K+ channels.

PubMed

Pragl, Bernt; Koschak, Alexandra; Trieb, Maria; Obermair, Gerald; Kaufmann, Walter A; Gerster, Uli; Blanc, Eric; Hahn, Christoph; Prinz, Heino; Schütz, Gerhard; Darbon, Herve; Gruber, Hermann J; Knaus, Hans-Günther

2002-01-01

Hongotoxin(1) (HgTX(1)), a 39-residue peptide recently isolated from the venom of Centruroides limbatus, blocks the voltage-gated K+ channels K(v)1.1, K(v)1.2, and K(v)1.3 at picomolar toxin concentrations (Koschak, A., Bugianesi, R. M., Mitterdorfer, J., Kaczorowski, G. J., Garcia, M. L., and Knaus, H. G. (1998) J. Biol. Chem. 273, 2639-2644). In this report, we determine the three-dimensional structure of HgTX(1) using NMR spectroscopy (PDB-code: 1HLY). HgTX(1) was found to possess a structure similar to previously characterized K+ channel toxins (e.g. margatoxin) consisting of a three-stranded antiparallel beta-sheet (residues 2-4, 26-30, and 33-37) and a helical conformation (part 3(10) helix and part alpha helix; residues 10-20). Due to the importance of residue Lys-28 for high-affinity interaction with the respective channels, lysine-reactive fluorescence dyes cannot be used to label wild-type HgTX(1). On the basis of previous studies (see above) and our NMR data, a HgTX(1) mutant (HgTX(1)-A19C) was engineered, expressed, and purified. HgTX(1)-A19C-SH was labeled using sulfhydryl-reactive Cy3-, Cy5-, and Alexa-dyes. Pharmacological characterization of fluorescently labeled HgTX(1)-A19C in radioligand binding studies indicated that these hongotoxin(1) analogues retain high-affinity for voltage-gated K+ channels and a respective pharmacological profile. Cy3- and Alexa-dye-labeled hongotoxin(1) analogues were used to investigate the localization of K+ channels in brain sections. The distribution of toxin binding closely follows the distribution of K(v)1.2 immunoreactivity with the highest expression levels in the cerebellar Purkinje cell layer. Taken together, these results demonstrate that fluorescently labeled HgTX(1) analogues comprise novel probes to characterize a subset of voltage-gated K+ channels.

Description of the first fungal dye-decolorizing peroxidase oxidizing manganese(II)

DOE PAGES

Fernandez-Fueyo, Elena; Linde, Dolores; Almendral, David; ...

2015-05-13

Two phylogenetically divergent genes of the new family of dye-decolorizing peroxidases (DyPs) were found during comparison of the four DyP genes identified in the Pleurotus ostreatus genome with over 200 DyP genes from other basidiomycete genomes. The heterologously expressed enzymes ( Pleos-DyP1 and Pleos-DyP4, following the genome nomenclature) efficiently oxidize anthraquinoid dyes (such as Reactive Blue 19), which are characteristic DyP substrates, as well as low redox-potential dyes (such as 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) and substituted phenols. However, only Pleos-DyP4 oxidizes the high redox-potential dye Reactive Black 5, at the same time that it displays high thermal and pH stability. Unexpectedly, bothmore » enzymes also oxidize Mn 2+ to Mn 3+, albeit with very different catalytic efficiencies. Pleos-DyP4 presents a Mn 2+ turnover (56 s –1) nearly in the same order of the two other Mn 2+-oxidizing peroxidase families identified in the P. ostreatus genome: manganese peroxidases (100 s–1 average turnover) and versatile peroxidases (145 s –1 average turnover), whose genes were also heterologously expressed. Oxidation of Mn 2+ has been reported for an Amycolatopsis DyP (24 s –1) and claimed for other bacterial DyPs, albeit with lower activities, but this is the first time that Mn 2+ oxidation is reported for a fungal DyP. Interestingly, Pleos-DyP4 (together with ligninolytic peroxidases) is detected in the secretome of P. ostreatus grown on different lignocellulosic substrates. In conclusion, it is suggested that generation of Mn 3+ oxidizers plays a role in the P. ostreatus white-rot lifestyle since three different families of Mn 2+-oxidizing peroxidase genes are present in its genome being expressed during lignocellulose degradation.« less

Description of the first fungal dye-decolorizing peroxidase oxidizing manganese(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernandez-Fueyo, Elena; Linde, Dolores; Almendral, David

Two phylogenetically divergent genes of the new family of dye-decolorizing peroxidases (DyPs) were found during comparison of the four DyP genes identified in the Pleurotus ostreatus genome with over 200 DyP genes from other basidiomycete genomes. The heterologously expressed enzymes ( Pleos-DyP1 and Pleos-DyP4, following the genome nomenclature) efficiently oxidize anthraquinoid dyes (such as Reactive Blue 19), which are characteristic DyP substrates, as well as low redox-potential dyes (such as 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) and substituted phenols. However, only Pleos-DyP4 oxidizes the high redox-potential dye Reactive Black 5, at the same time that it displays high thermal and pH stability. Unexpectedly, bothmore » enzymes also oxidize Mn 2+ to Mn 3+, albeit with very different catalytic efficiencies. Pleos-DyP4 presents a Mn 2+ turnover (56 s –1) nearly in the same order of the two other Mn 2+-oxidizing peroxidase families identified in the P. ostreatus genome: manganese peroxidases (100 s–1 average turnover) and versatile peroxidases (145 s –1 average turnover), whose genes were also heterologously expressed. Oxidation of Mn 2+ has been reported for an Amycolatopsis DyP (24 s –1) and claimed for other bacterial DyPs, albeit with lower activities, but this is the first time that Mn 2+ oxidation is reported for a fungal DyP. Interestingly, Pleos-DyP4 (together with ligninolytic peroxidases) is detected in the secretome of P. ostreatus grown on different lignocellulosic substrates. In conclusion, it is suggested that generation of Mn 3+ oxidizers plays a role in the P. ostreatus white-rot lifestyle since three different families of Mn 2+-oxidizing peroxidase genes are present in its genome being expressed during lignocellulose degradation.« less

Diketopyrrolopyrrole: brilliant red pigment dye-based fluorescent probes and their applications.

PubMed

Kaur, Matinder; Choi, Dong Hoon

2015-01-07

The development of fluorescent probes for the detection of biologically relevant species is a burgeoning topic in the field of supramolecular chemistry. A number of available dyes such as rhodamine, coumarin, fluorescein, and cyanine have been employed in the design and synthesis of new fluorescent probes. However, diketopyrrolopyrrole (DPP) and its derivatives have a distinguished role in supramolecular chemistry for the design of fluorescent dyes. DPP dyes offer distinctive advantages relative to other organic dyes, including high fluorescence quantum yields and good light and thermal stability. Significant advancements have been made in the development of new fluorescent probes based on DPP in recent years as a result of tireless research efforts by the chemistry scientific community. In this tutorial review, we highlight the recent progress in the development of DPP-based fluorescent probes for the period spanning 2009 to the present time and the applications of these probes to recognition of biologically relevant species including anions, cations, reactive oxygen species, thiols, gases and other miscellaneous applications. This review is targeted toward providing the readers with deeper understanding for the future design of DPP-based fluorogenic probes for chemical and biological applications.

Dyes removal using activated carbon from palm oil waste with digital image colorimetry quantification

NASA Astrophysics Data System (ADS)

Firdaus, M. Lutfi; Puspita, Melfi; Alwi, Wiwit; Ghufira, Nurhamidah, Elvia, Rina

2017-11-01

In the present study, activated carbon prepared from palm oil husk was used as adsorbent to remove synthetic dyes of Reactive Red 120 (RR) and Direct Green 26 (DG) from aqueous solution. The effects of solution pH, contact time, adsorbent weight, dyes concentration, and temperature on adsorption were evaluated based on batch experiments along with determination of the adsorption isotherms, kinetics, and thermodynamics parameters. Visible spectrophotometry was used for the quantification of dyes concentration, in conjunction with digital image colorimetry as a novel quantification method. Compared to visible spectrophotometry, the results of digital image colorimetry were accurate. In addition, improved sensitivity was achieved using this new colorimetry method. At equilibrium, dyes adsorption onto activated carbon followed Freundlich model, with adsorption capacities for RR and DG were 32 and 27 mg/g, respectively. The adsorption kinetics study showed a pseudo-second-order model with thermodynamic parameters of ΔG°, ΔH°, and ΔS° were -1.8 to -3.8 kJ/mol, -13.5 to -24.38 kJ/mol, and 0.001 J/mol, respectively. Therefore, the process of adsorption was exothermic and spontaneous with an increase in the disorder or entropy of the system.

Experimental and theoretical study using DFT method for the competitive adsorption of two cationic dyes from wastewaters

NASA Astrophysics Data System (ADS)

Regti, Abdelmajid; Ayouchia, Hicham Ben El; Laamari, My Rachid; Stiriba, Salah Eddine; Anane, Hafid; Haddad, Mohammadine El

2016-12-01

The adsorption of cationic dyes, Basic Yellow (BY28) and Methylene Blue (MB) on a new activated carbon from medlar species were studied in both single and binary system. Some experimental parameters, namely, pH, amount of adsorbent and contact time are studied. Quantum chemical results indicate that the adsorption efficiency was directly related to the dye electrophilicity power. Some theorical parameters were calculated and proved that MB is more electrophilic than BY28, than greatest interaction with surface sites. Kinetic study showed that the adsorption follows the pseudo-second-order model and Freundlich was the best model to describe the phenomenon in the single and binary system. According to the local reactivity results using Parr functions, the sulphur and nitrogen atoms will be the main adsorption sites.

Systemic reduction of rice blast by means of photosensitizers

USDA-ARS?s Scientific Manuscript database

Acquired disease resistance of plants may be induced by exogenous reactive oxygen species or their sources. Certain compounds (photosensitizers) produce ROS at the expense of light energy. This study used photodynamic dyes bengal rose and methylene blue, which yield singlet oxygen, and mercaptopyrid...

Fixed-bed adsorption of reactive azo dye onto granular activated carbon prepared from waste.

PubMed

Ahmad, A A; Hameed, B H

2010-03-15

In this work, the adsorption potential of bamboo waste based granular activated carbon (BGAC) to remove C.I. Reactive Black (RB5) from aqueous solution was investigated using fixed-bed adsorption column. The effects of inlet RB5 concentration (50-200mg/L), feed flow rate (10-30 mL/min) and activated carbon bed height (40-80 mm) on the breakthrough characteristics of the adsorption system were determined. The highest bed capacity of 39.02 mg/g was obtained using 100mg/L inlet dye concentration, 80 mm bed height and 10 mL/min flow rate. The adsorption data were fitted to three well-established fixed-bed adsorption models namely, Adam's-Bohart, Thomas and Yoon-Nelson models. The results fitted well to the Thomas and Yoon-Nelson models with coefficients of correlation R(2)>or=0.93 at different conditions. The BGAC was shown to be suitable adsorbent for adsorption of RB5 using fixed-bed adsorption column. (c) 2009 Elsevier B.V. All rights reserved.

Decolorization and degradation of reactive yellow HF aqueous solutions by electrochemical advanced oxidation processes.

PubMed

Bedolla-Guzman, A; Feria-Reyes, R; Gutierrez-Granados, S; Peralta-Hernández, Juan M

2017-05-01

Textile manufacturing is the one responsible for water bodies' contamination through the discharge of colored wastes. This work presents the study of reactive yellow HF (RYHF) dye degradation under two different electrochemical advanced oxidation processes (EAOP), namely anodic oxidation (AO) and electro-Fenton (EF)/boron-doped diamond (BDD) process. For the AO, 100 and 300 mg/L solutions using Pt and BDD as anodes in a 100 mL stirred tank cell were used, with a supporting electrolyte of 0.05 mol/L of Na 2 SO 4 at pH 3 under 30 and 50 mA/cm 2 current density. The EF/BDD process was carried out in a flow reactor at 4 and 7 L/min to degrade 100, 200, and 300 mg/L RYHF solutions under 50 and 80 mA/cm 2 . UV-Vis determinations were used for decolorization evaluation, while high-performance liquid chromatography (HPLC) method provided information on dye degradation rate.

Treatment of synthetic textile wastewater containing dye mixtures with microcosms.

PubMed

Yaseen, Dina A; Scholz, Miklas

2018-01-01

The aim was to assess the ability of microcosms (laboratory-scale shallow ponds) as a post polishing stage for the remediation of artificial textile wastewater comprising two commercial dyes (basic red 46 (BR46) and reactive blue 198 (RB198)) as a mixture. The objectives were to evaluate the impact of Lemna minor L. (common duckweed) on the water quality outflows; the elimination of dye mixtures, organic matter, and nutrients; and the impact of synthetic textile wastewater comprising dye mixtures on the L. minor plant growth. Three mixtures were prepared providing a total dye concentration of 10 mg/l. Findings showed that the planted simulated ponds possess a significant (p < 0.05) potential for improving the outflow characteristics and eliminate dyes, ammonium-nitrogen (NH 4 -N), and nitrate-nitrogen (NO 3 -N) in all mixtures compared with the corresponding unplanted ponds. The removal of mixed dyes in planted ponds was mainly due to phyto-transformation and adsorption of BR46 with complete aromatic amine mineralisation. For ponds containing 2 mg/l of RB198 and 8 mg/l of BR46, removals were around 53%, which was significantly higher than those for other mixtures: 5 mg/l of RB198 and 5 mg/l of BR46 and 8 mg/l of RB198 and 2 mg/l of BR46 achieved only 41 and 26% removals, respectively. Dye mixtures stopped the growth of L. minor, and the presence of artificial wastewater reduced their development.

Biphasic reduction model for predicting the impacts of dye-bath constituents on the reduction of tris-azo dye Direct Green-1 by zero valent iron (Fe0).

PubMed

Kumar, Raja; Sinha, Alok

2017-02-01

Influence of common dye-bath additives, namely sodium chloride, ammonium sulphate, urea, acetic acid and citric acid, on the reductive decolouration of Direct Green 1 dye in the presence of Fe 0 was investigated. Organic acids improved dye reduction by augmenting Fe 0 corrosion, with acetic acid performing better than citric acid. NaCl enhanced the reduction rate by its 'salting out' effect on the bulk solution and by Cl - anion-mediated pitting corrosion of iron surface. (NH 4 ) 2 SO 4 induced 'salting out' effect accompanied by enhanced iron corrosion by SO 4 2- anion and buffering effect of NH 4 + improved the reduction rates. However, at 2g/L (NH 4 ) 2 SO 4 concentration, complexating of SO 4 2- with iron oxides decreased Fe 0 reactivity. Urea severely compromised the reduction reaction, onus to its chaotropic and 'salting in' effect in solution, and due to it masking the Fe 0 surface. Decolouration obeyed biphasic reduction kinetics (R 2 >0.993 in all the cases) exhibiting an initial rapid phase, when more than 95% dye reduction was observed, preceding a tedious phase. Maximum rapid phase reduction rate of 0.955/min was observed at pH2 in the co-presence of all dye-bath constituents. The developed biphasic model reckoned the influence of each dye-bath additive on decolouration and simulated well with the experimental data obtained at pH2. Copyright © 2016. Published by Elsevier B.V.

Reprint Characteristics of Non-Silver Films.

ERIC Educational Resources Information Center

Microform Review, 1990

1990-01-01

Describes reprint characteristics of diazo and vesicular films. Use with microform reader-printers and autogeneration of copies are discussed, and methods of dealing with the unusual reprint behavior of these films are outlined. (MES)

Dimensioning the Term Carbenoid.

PubMed

Caballero, Ana; Pérez, Pedro J

2017-10-17

The current use of the term carbenoid is discussed, particularly in the context of carbene transfer reactions from diazo compounds, in which intermediates of type L n M=CR 1 R 2 , or one of its resonance forms, are tagged which such a name. We discuss this issue, on the basis of the data evidencing the metal-carbene nature of those intermediates, as well as the existence of carbenoids of type (N 2 )(M)CR 1 R 2 en route to the formation to L n M=CR 1 R 2' from diazo reagents. We propose the exclusive use of the carbenoid term to species of type (X)(M)CR 1 R 2 with a tetrasubstituted carbon center that upon loss of X afford an effective carbene transfer process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Functionalized Pyrazoles via 1,3-Dipolar Cycloaddition of α-Diazo-β-ketophosphonates, Sufones and Esters with Electron-Deficient Alkenes.

PubMed

Baiju, T V; Namboothiri, Irishi N N

2017-10-01

1,3-Dipolar cycloaddition of diazo compounds with olefinic substrates is a promising atom-economic strategy for the construction of functionalized pyrazoles. Over the last few years, our group has been engaged in the synthesis of phosphonyl/sulfonylpyrazoles and pyrazole esters by employing Bestmann-Ohira Reagent (BOR) and its sulfur and ester analogs as 1,3-dipole precursors with various dipolarophiles. This account describes the novel synthetic methods developed in our laboratory, in the perspective of closely related work by others, for the synthesis of phosphonyl/sulfonylpyrazoles, pyrazole esters and the total synthesis of Withasomnine, a natural product, by using 1,3-dipolar cycloaddition as the key step. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-performance liquid chromatography determination of ketone bodies in human plasma by precolumn derivatization with p-nitrobenzene diazonium fluoroborate.

PubMed

Yamato, Susumu; Shinohara, Kumiko; Nakagawa, Saori; Kubota, Ai; Inamura, Katsushi; Watanabe, Gen; Hirayama, Satoshi; Miida, Takashi; Ohta, Shin

2009-01-01

We developed and validated a sensitive and convenient high-performance liquid chromatography (HPLC) method for the specific determination of ketone bodies (acetoacetate and D-3-hydroxybutyrate) in human plasma. p-Nitrobenzene diazonium fluoroborate (diazo reagent) was used as a precolumn derivatization agent, and 3-(2-hydroxyphenyl) propionic acid was used as an internal standard. After the reaction, excess diazo reagent and plasma proteins were removed by passing through a solid-phase cartridge (C(18)). The derivatives retained on the cartridge were eluted with methanol, introduced into the HPLC system, and then detected with UV at 380 nm. A calibration curve for acetoacetate standard solution with a 20-microl injection volume showed good linearity in the range of 1 to 400 microM with a 0.9997 correlation coefficient. For the determination of D-3-hydroxybutyrate, it was converted to acetoacetate before reaction with the diazo reagent by an enzymatic coupling method using D-3-hydroxybutyrate dehydrogenase and lactate dehydrogenase. A calibration curve for D-3-hydroxybutyrate standard solution also showed good linearity in the range of 1.5 to 2000 microM with a 0.9988 correlation coefficient. Analytical recoveries of acetoacetate and D-3-hydroxybutyrate in human plasma were satisfactory. The method was successfully applied to samples from diabetic patients, and results were consistent with those obtained using the thio-NAD enzymatic cycling method used in clinical laboratories.

Overexpression of a novel thermostable and chloride-tolerant laccase from Thermus thermophilus SG0.5JP17-16 in Pichia pastoris and its application in synthetic dye decolorization.

PubMed

Liu, Huiping; Cheng, Yu; Du, Bing; Tong, Chaofan; Liang, Shuli; Han, Shuangyan; Zheng, Suiping; Lin, Ying

2015-01-01

Laccases have been used for the decolorization and detoxification of synthetic dyes due to their ability to oxidize a wide variety of dyes with water as the sole byproduct. A putative laccase gene (LacTT) from Thermus thermophilus SG0.5JP17-16 was screened using the genome mining approach, and it was highly expressed in Pichia pastoris, yielding a high laccase activity of 6130 U/L in a 10-L fermentor. The LacTT open reading frame encoded a protein of 466 amino acid residues with four putative Cu-binding regions. The optimal pH of the recombinant LacTT was 4.5, 6.0, 7.5 and 8.0 with 2,2'-azino-bis(3-ethylbenzothazoline-6-sulfonic acid) (ABTS), syringaldazine (SGZ), guaiacol, and 2,6-dimethoxyphenol (2,6-DMP) as the substrate, respectively. The optimal temperature of LacTT was 90°C with guaiacol as the substrate. LacTT was highly stable at pH 4.0-11.0 and thermostable at 40°C-90°C, confirming that it is a pH-stable and thermostable laccase. Furthermore, LacTT also exhibited high tolerance to halides such as NaCl, NaBr and NaF, and decolorized 100%, 94%, 94% and 73% of Congo Red, Reactive Black B and Reactive Black WNN, and Remazol Brilliant Blue R, respectively. Interestingly, addition of high concentration of NaCl increased the RBBR decolorization efficiency of LacTT. These results suggest that LacTT is a good candidate for industrial applications such as dyestuff processing and degradation of dyes in textile wastewaters.

Overexpression of a Novel Thermostable and Chloride-Tolerant Laccase from Thermus thermophilus SG0.5JP17-16 in Pichia pastoris and Its Application in Synthetic Dye Decolorization

PubMed Central

Liu, Huiping; Cheng, Yu; Du, Bing; Tong, Chaofan; Liang, Shuli; Han, Shuangyan; Zheng, Suiping; Lin, Ying

2015-01-01

Laccases have been used for the decolorization and detoxification of synthetic dyes due to their ability to oxidize a wide variety of dyes with water as the sole byproduct. A putative laccase gene (LacTT) from Thermus thermophilus SG0.5JP17-16 was screened using the genome mining approach, and it was highly expressed in Pichia pastoris, yielding a high laccase activity of 6130 U/L in a 10-L fermentor. The LacTT open reading frame encoded a protein of 466 amino acid residues with four putative Cu-binding regions. The optimal pH of the recombinant LacTT was 4.5, 6.0, 7.5 and 8.0 with 2,2'-azino-bis(3-ethylbenzothazoline-6-sulfonic acid) (ABTS), syringaldazine (SGZ), guaiacol, and 2,6-dimethoxyphenol (2,6-DMP) as the substrate, respectively. The optimal temperature of LacTT was 90°C with guaiacol as the substrate. LacTT was highly stable at pH 4.0–11.0 and thermostable at 40°C–90°C, confirming that it is a pH-stable and thermostable laccase. Furthermore, LacTT also exhibited high tolerance to halides such as NaCl, NaBr and NaF, and decolorized 100%, 94%, 94% and 73% of Congo Red, Reactive Black B and Reactive Black WNN, and Remazol Brilliant Blue R, respectively. Interestingly, addition of high concentration of NaCl increased the RBBR decolorization efficiency of LacTT. These results suggest that LacTT is a good candidate for industrial applications such as dyestuff processing and degradation of dyes in textile wastewaters. PMID:25790466

Sorption and desorption studies of a reactive azo dye on effective disposal of redundant material.

PubMed

Çelekli, Abuzer; Bozkurt, Hüseyin

2013-07-01

The effective disposal of redundant elephant dung (ED) is important for environmental protection and utilization of resource. The aim of this study was to remove a toxic-azo dye, Reactive Red (RR) 120, using this relatively cheap material as a new adsorbent. The FTIR-ATR spectra of ED powders before and after the sorption of RR 120 and zero point charge (pHzpc) of ED were determined. The sorption capacity of ED for removing of RR 120 were carried out as functions of particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. Sorption isotherm, kinetic, activation energy, thermodynamic, and desorption parameters of RR 120 on ED were studied. The sorption process was found to be dependent on particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. FTIR-ATR spectroscopy indicated that amine and amide groups have significant role on the sorption of RR 120 on ED. The pHzpc of ED was found to be 7.3. Sorption kinetic of RR 120 on ED was well described by sigmoidal Logistic model. The Langmuir isotherm was well fitted to the equilibrium data. The maximum sorption capacity was 95.71 mg g(-1). The sorption of RR 120 on ED was mainly physical and exothermic according to results of D-R isotherm, Arrhenius equation, thermodynamic, and desorption studies. The thermodynamic parameters showed that this process was feasible and spontaneous. This study showed that ED as a low-cost adsorbent had a great potential for the removal of RR 120 as an alternative eco-friendly process.

Micro-encapsulated sensors for in vivo assessment of the oxidative stress in aquatic organisms

NASA Astrophysics Data System (ADS)

Sadovoy, Anton; Teh, Cathleen; Escobar, Marco; Meglinski, Igor; Korzh, Vladimir

2011-10-01

Oxidative stress results from an imbalance between the production and detoxification of reactive oxygen spices (ROS). ROS are natural byproducts of normal metabolism of oxygen and have important roles in cell signaling and homeostasis. Many heart related diseases like heart failure and myocardial infarction develop as a result of oxidative stress. Current treatment cannot improve the progressive decline in heart function experienced by all patients. Therefore heart failure is the cause of around 25% of all deaths in the Asia Pacific region. Thus any step taken to address the oxidative stress problem is essential for enhancing human health and improve their quality of life. Current approach is dedicated to develop micron-size oxidation stress-sensor for in-vivo measuring level of ROS in KillerRed expressing transgenic zebrafish larvae. Central to our investigation is the light-inducible heart failure animal model we developed in zebrafish that expressed KillerRed in the heart. By utilizing the photosensitizer properties of KillerRed to produce ROS upon green light illumination, heart failure can be repeatedly induced in a non-invasive manner. Importantly, the use of this biological platform permits the development of physiologically sensitive ROS sensor and identifies efficient antioxidants that improve heart contractility. The biosensor approach is based on utilizing biocompatible polyelectrolyte microcapsules as a carry of fluorescent dyes sensitive to amount of reactive oxygen spices. Microcapsule prevents dye diffusion in tissue that makes use toxic dyes possible. Microcapsule's wall is permeable for environment with size less than 500 Da. The oxidation stress-sensors are injected directly in zebrafish pericardium with further circulation along blood system. Detecting of ROS is obtained by using laser scanning microscopy by illuminating oxidation stress-sensors and detecting changing excitation signal from the fluorescent dye.

Micro-encapsulated sensors for in vivo assessment of the oxidative stress in aquatic organisms

NASA Astrophysics Data System (ADS)

Sadovoy, Anton; Teh, Cathleen; Escobar, Marco; Meglinski, Igor; Korzh, Vladimir

2012-03-01

Oxidative stress results from an imbalance between the production and detoxification of reactive oxygen spices (ROS). ROS are natural byproducts of normal metabolism of oxygen and have important roles in cell signaling and homeostasis. Many heart related diseases like heart failure and myocardial infarction develop as a result of oxidative stress. Current treatment cannot improve the progressive decline in heart function experienced by all patients. Therefore heart failure is the cause of around 25% of all deaths in the Asia Pacific region. Thus any step taken to address the oxidative stress problem is essential for enhancing human health and improve their quality of life. Current approach is dedicated to develop micron-size oxidation stress-sensor for in-vivo measuring level of ROS in KillerRed expressing transgenic zebrafish larvae. Central to our investigation is the light-inducible heart failure animal model we developed in zebrafish that expressed KillerRed in the heart. By utilizing the photosensitizer properties of KillerRed to produce ROS upon green light illumination, heart failure can be repeatedly induced in a non-invasive manner. Importantly, the use of this biological platform permits the development of physiologically sensitive ROS sensor and identifies efficient antioxidants that improve heart contractility. The biosensor approach is based on utilizing biocompatible polyelectrolyte microcapsules as a carry of fluorescent dyes sensitive to amount of reactive oxygen spices. Microcapsule prevents dye diffusion in tissue that makes use toxic dyes possible. Microcapsule's wall is permeable for environment with size less than 500 Da. The oxidation stress-sensors are injected directly in zebrafish pericardium with further circulation along blood system. Detecting of ROS is obtained by using laser scanning microscopy by illuminating oxidation stress-sensors and detecting changing excitation signal from the fluorescent dye.

Efficient Site-Specific Labeling of Proteins via Cysteines

PubMed Central

Kim, Younggyu; Ho, Sam O.; Gassman, Natalie R.; Korlann, You; Landorf, Elizabeth V.; Collart, Frank R.; Weiss, Shimon

2011-01-01

Methods for chemical modifications of proteins have been crucial for the advancement of proteomics. In particular, site-specific covalent labeling of proteins with fluorophores and other moieties has permitted the development of a multitude of assays for proteome analysis. A common approach for such a modification is solvent-accessible cysteine labeling using thiol-reactive dyes. Cysteine is very attractive for site-specific conjugation due to its relative rarity throughout the proteome and the ease of its introduction into a specific site along the protein's amino acid chain. This is achieved by site-directed mutagenesis, most often without perturbing the protein's function. Bottlenecks in this reaction, however, include the maintenance of reactive thiol groups without oxidation before the reaction, and the effective removal of unreacted molecules prior to fluorescence studies. Here, we describe an efficient, specific, and rapid procedure for cysteine labeling starting from well-reduced proteins in the solid state. The efficacy and specificity of the improved procedure are estimated using a variety of single-cysteine proteins and thiol-reactive dyes. Based on UV/vis absorbance spectra, coupling efficiencies are typically in the range 70–90%, and specificities are better than ~95%. The labeled proteins are evaluated using fluorescence assays, proving that the covalent modification does not alter their function. In addition to maleimide-based conjugation, this improved procedure may be used for other thiol-reactive conjugations such as haloacetyl, alkyl halide, and disulfide interchange derivatives. This facile and rapid procedure is well suited for high throughput proteome analysis. PMID:18275130

Efficient site-specific labeling of proteins via cysteines.

PubMed

Kim, Younggyu; Ho, Sam O; Gassman, Natalie R; Korlann, You; Landorf, Elizabeth V; Collart, Frank R; Weiss, Shimon

2008-03-01

Methods for chemical modifications of proteins have been crucial for the advancement of proteomics. In particular, site-specific covalent labeling of proteins with fluorophores and other moieties has permitted the development of a multitude of assays for proteome analysis. A common approach for such a modification is solvent-accessible cysteine labeling using thiol-reactive dyes. Cysteine is very attractive for site-specific conjugation due to its relative rarity throughout the proteome and the ease of its introduction into a specific site along the protein's amino acid chain. This is achieved by site-directed mutagenesis, most often without perturbing the protein's function. Bottlenecks in this reaction, however, include the maintenance of reactive thiol groups without oxidation before the reaction, and the effective removal of unreacted molecules prior to fluorescence studies. Here, we describe an efficient, specific, and rapid procedure for cysteine labeling starting from well-reduced proteins in the solid state. The efficacy and specificity of the improved procedure are estimated using a variety of single-cysteine proteins and thiol-reactive dyes. Based on UV/vis absorbance spectra, coupling efficiencies are typically in the range 70-90%, and specificities are better than approximately 95%. The labeled proteins are evaluated using fluorescence assays, proving that the covalent modification does not alter their function. In addition to maleimide-based conjugation, this improved procedure may be used for other thiol-reactive conjugations such as haloacetyl, alkyl halide, and disulfide interchange derivatives. This facile and rapid procedure is well suited for high throughput proteome analysis.

Decolorization of complex dyes and textile effluent by extracellular enzymes of Cyathus bulleri cultivated on agro-residues/domestic wastes and proposed pathway of degradation of Kiton blue A and reactive orange 16.

PubMed

Vats, Arpita; Mishra, Saroj

2017-04-01

In this study, the white-rot fungus Cyathus bulleri was cultivated on low-cost agro-residues, namely wheat bran (WB), wheat straw (WS), and domestic waste orange peel (OP) for production of ligninolytic enzymes. Of the three substrates, WB and OP served as good materials for the production of laccase with no requirement of additional carbon or nitrogen source. Specific laccase activity of 94.4 U mg -1 extracellular protein and 21.01 U mg -1 protein was obtained on WB and OP, respectively. Maximum decolorization rate of 13.6 μmol h -1  U -1 laccase for reactive black 5 and 22.68 μmol h -1  U -1 laccase for reactive orange 16 (RO) was obtained with the WB culture filtrate, and 11.7 μmol h -1  U -1 laccase for reactive violet 5 was observed with OP culture filtrate. Importantly, Kiton blue A (KB), reported not to be amenable to enzymatic degradation, was degraded by culture filtrate borne activities. Products of degradation of KB and RO were identified by mass spectrometry, and a pathway of degradation proposed. WB-grown culture filtrate decolorized and detoxified real and simulated textile effluents by about 40%. The study highlights the use of inexpensive materials for the production of enzymes effective on dyes and effluents.

Synthesis of novel reactive N-halamine precursors and application in antimicrobial cellulose

NASA Astrophysics Data System (ADS)

Jiang, Zhiming; Ma, Kaikai; Du, Jinmei; Li, Rong; Ren, Xuehong; Huang, T. S.

2014-01-01

2,4,6-Trichloro-s-triazine has been used as one of the important linkers of reactive dyes for textiles such as cellulosic fibers. N-Halamine precursors could be bonded to a triazine-based linker by the chloride displacement reaction, and the synthesized compounds could attach to cotton fabrics by covalent bonds through a reactive dyeing process. In this study, two novel antimicrobial N-halamine precursors, 2,2,6,6-tetramethyl-4-piperidinol-s-trizine (TMPT) and 4-(4-(2,2,6,6-tetramethyl-4-piperidinol)-6-chloro-1,3,5-triazinylamino)-benzenesulfonate (BTMPT), were synthesized and used to coat cotton fabrics. The synthesized s-triazine-based N-halamine precursors react with cellulose to produce biocidal cellulosic fibers upon exposure to diluted household bleach. The coated fabrics were characterized by FT-IR and SEM. The chlorinated treated cotton swatches demonstrated excellent antimicrobial properties against S. aureus (Gram-positive) and E. coli O157:H7 (Gram-negative) with short contact times. Washing test and UVA light test showed that chlorinated BTMPT-coated cotton fabrics were more stable than TMPT-coated cotton fabrics. Compared to the traditional pad-dry-cure technique to produce antimicrobial textiles, the novel process in this study has advantages of saving energy and maintaining tensile strength of fabrics.

Voltage-sensitive styryl dyes as singlet oxygen targets on the surface of bilayer lipid membrane.

PubMed

Sokolov, V S; Gavrilchik, A N; Kulagina, A O; Meshkov, I N; Pohl, P; Gorbunova, Yu G

2016-08-01

Photosensitizers are widely used as photodynamic therapeutic agents killing cancer cells by photooxidation of their components. Development of new effective photosensitive molecules requires profound knowledge of possible targets for reactive oxygen species, especially for its singlet form. Here we studied photooxidation of voltage-sensitive styryl dyes (di-4-ANEPPS, di-8-ANEPPS, RH-421 and RH-237) by singlet oxygen on the surface of bilayer lipid membranes commonly used as cell membrane models. Oxidation was induced by irradiation of a photosensitizer (aluminum phthalocyanine tetrasulfonate) and monitored by the change of dipole potential on the surface of the membrane. We studied the drop of the dipole potential both in the case when the dye molecules were adsorbed on the same side of the lipid bilayer as the photosensitizer (cis-configuration) and in the case when they were adsorbed on the opposite side (trans-configuration). Based on a simple model, we determined the rate of oxidation of the dyes from the kinetics of change of the potential during and after irradiation. This rate is proportional to steady-state concentration of singlet oxygen in the membrane under irradiation. Comparison of the oxidation rates of various dyes reveals that compounds of ANEPPS series are more sensitive to singlet oxygen than RH type dyes, indicating that naphthalene group is primarily responsible for their oxidation. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, characterization, and reactivity of cellulose modified nano zero-valent iron for dye discoloration

NASA Astrophysics Data System (ADS)

Wang, Xiangyu; Wang, Pei; Ma, Jun; Liu, Huiling; Ning, Ping

2015-08-01

Nano zero-valent iron (NZVI) was innovatively and successfully modified by using hydroxyethyl cellulose (HEC) and hydroxypropylmethyl cellulose (HPMC) as dispersants. The systematic characterization observations (including XRD, SEM and TEM) illustrate that, compared with bare nano zero-valent iron particles (BNZVI), the particle sizes of hydroxyethyl cellulose modified (ENZVI) and hydroxypropylmethyl cellulose modified (PNZVI) were decreased, while the dispersity and antioxidizability of ENZVI and PNZVI particles were increased. The discoloration efficiencies of ENZVI, PNZVI, and BNZVI were compared by using dyes (including orange II, methyl orange, methyl blue, and methylene blue) as target pollutant. The results show that both the discoloration efficiency and reaction rate of ENZVI and PNZVI are higher than that of BNZVI. In addition, effects of dispersant content, dye type, pH value, initial dye concentration, iron dosage, and reaction temperature on discoloration efficiencies were studied. The results show that discoloration efficiency was decreased by increasing initial pH value and dye concentration, and it was increased with the increase the iron dosage and reaction temperature. Under optimized NZVI addition of 0.7 g L-1, the discoloration efficiencies of ENZVI and PNZVI were increased to 96.33% and 98.62%, respectively. And the possible discoloration pathway and dispersant modification mechanism of NZVI were discussed. This study suggests hydroxyethyl cellulose and hydroxypropylmethyl cellulose dispersed NZVI can be utilized as a promising modified nano-material for degradation of dye wastewater.

Determination of the mass transfer limiting step of dye adsorption onto commercial adsorbent by using mathematical models.

PubMed

Marin, Pricila; Borba, Carlos Eduardo; Módenes, Aparecido Nivaldo; Espinoza-Quiñones, Fernando R; de Oliveira, Silvia Priscila Dias; Kroumov, Alexander Dimitrov

2014-01-01

Reactive blue 5G dye removal in a fixed-bed column packed with Dowex Optipore SD-2 adsorbent was modelled. Three mathematical models were tested in order to determine the limiting step of the mass transfer of the dye adsorption process onto the adsorbent. The mass transfer resistance was considered to be a criterion for the determination of the difference between models. The models contained information about the external, internal, or surface adsorption limiting step. In the model development procedure, two hypotheses were applied to describe the internal mass transfer resistance. First, the mass transfer coefficient constant was considered. Second, the mass transfer coefficient was considered as a function of the dye concentration in the adsorbent. The experimental breakthrough curves were obtained for different particle diameters of the adsorbent, flow rates, and feed dye concentrations in order to evaluate the predictive power of the models. The values of the mass transfer parameters of the mathematical models were estimated by using the downhill simplex optimization method. The results showed that the model that considered internal resistance with a variable mass transfer coefficient was more flexible than the other ones and this model described the dynamics of the adsorption process of the dye in the fixed-bed column better. Hence, this model can be used for optimization and column design purposes for the investigated systems and similar ones.

The Diazo Copying Process.

ERIC Educational Resources Information Center

Osterby, Bruce

1989-01-01

Described is an activity which demonstrates an organic-based reprographic method that is used extensively for the duplication of microfilm and engineering drawings. Discussed are the chemistry of the process and how to demonstrate the process for students. (CW)

Selective dye-labeling of newly synthesized proteins in bacterial cells.

PubMed

Beatty, Kimberly E; Xie, Fang; Wang, Qian; Tirrell, David A

2005-10-19

We describe fluorescence labeling of newly synthesized proteins in Escherichia coli cells by means of Cu(I)-catalyzed cycloaddition between alkynyl amino acid side chains and the fluorogenic dye 3-azido-7-hydroxycoumarin. The method involves co-translational labeling of proteins by the non-natural amino acids homopropargylglycine (Hpg) or ethynylphenylalanine (Eth) followed by treatment with the dye. As a demonstration, the model protein barstar was expressed and treated overnight with Cu(I) and 3-azido-7-hydroxycoumarin. Examination of treated cells by confocal microscopy revealed that strong fluorescence enhancement was observed only for alkynyl-barstar treated with Cu(I) and the reactive dye. The cellular fluorescence was punctate, and gel electrophoresis confirmed that labeled barstar was localized in inclusion bodies. Other proteins showed little fluorescence. Examination of treated cells by fluorimetry demonstrated that cultures supplemented with Eth or Hpg showed an 8- to 14-fold enhancement in fluorescence intensity after labeling. Addition of a protein synthesis inhibitor reduced the emission intensity to levels slightly above background, confirming selective labeling of newly synthesized proteins in the bacterial cell.

A novel multicopper oxidase (laccase) from cyanobacteria: Purification, characterization with potential in the decolorization of anthraquinonic dye.

PubMed

Afreen, Sumbul; Shamsi, Tooba Naz; Baig, Mohd Affan; Ahmad, Nadeem; Fatima, Sadaf; Qureshi, M Irfan; Hassan, Md Imtaiyaz; Fatma, Tasneem

2017-01-01

A novel extracellular laccase enzyme produced from Spirulina platensis CFTRI was purified by ultrafiltration, cold acetone precipitation, anion exchange and size exclusion chromatography with 51.5% recovery and 5.8 purification fold. The purified laccase was a monomeric protein with molecular mass of ~66 kDa that was confirmed by zymogram analysis and peptide mass fingerprinting. The optimum pH and temperature of the enzyme activity was found at 3.0 and 30°C using ABTS as substrate but the enzyme was quite stable at high temperature and alkaline pH. The laccase activity was enhanced by Cu+2, Zn+2 and Mn+2. In addition, the dye decolorization potential of purified laccase was much higher in terms of extent as well as time. The purified laccase decolorized (96%) of anthraquinonic dye Reactive blue- 4 within 4 h and its biodegradation studies was monitored by UV visible spectra, FTIR and HPLC which concluded that cyanobacterial laccase can be efficiently used to decolorize synthetic dye and help in waste water treatment.

A novel multicopper oxidase (laccase) from cyanobacteria: Purification, characterization with potential in the decolorization of anthraquinonic dye

PubMed Central

Afreen, Sumbul; Shamsi, Tooba Naz; Baig, Mohd Affan; Ahmad, Nadeem; Fatima, Sadaf; Qureshi, M. Irfan; Hassan, Md. Imtaiyaz

2017-01-01

A novel extracellular laccase enzyme produced from Spirulina platensis CFTRI was purified by ultrafiltration, cold acetone precipitation, anion exchange and size exclusion chromatography with 51.5% recovery and 5.8 purification fold. The purified laccase was a monomeric protein with molecular mass of ~66 kDa that was confirmed by zymogram analysis and peptide mass fingerprinting. The optimum pH and temperature of the enzyme activity was found at 3.0 and 30°C using ABTS as substrate but the enzyme was quite stable at high temperature and alkaline pH. The laccase activity was enhanced by Cu+2, Zn+2 and Mn+2. In addition, the dye decolorization potential of purified laccase was much higher in terms of extent as well as time. The purified laccase decolorized (96%) of anthraquinonic dye Reactive blue- 4 within 4 h and its biodegradation studies was monitored by UV visible spectra, FTIR and HPLC which concluded that cyanobacterial laccase can be efficiently used to decolorize synthetic dye and help in waste water treatment. PMID:28384218

Matrix-Isolation Spectroscopy of Reactive Organic Molecules of Relevance to Interstellar Space

NASA Astrophysics Data System (ADS)

Kopff, Laura A.; Nolan, Alex M.; Kreifels, Terese A.; Draxler, Thomas W.; Esselman, Brian J.; Burrmann, Nicola J.; McMahon, Robert J.

2010-11-01

Matrix isolation, the process of trapping a molecule in an inert gas at low temperature, provides a means for studying highly reactive intermediates, such as carbenes or radicals. Reactive species can be characterized by IR, UV-vis and/or EPR spectroscopy. Comparison of experimental and computed spectral data, as well as chemical reactivity, is used for structural assignment Triplet propynylidene is proposed to exist in the interstellar medium (ISM), due to the detection of a higher-energy isomers via rotational spectroscopy. Currently, we are exploring the structural and photochemical effects of varying substituents on the propynylidne system. A diazo precursor has been synthesized and photolyzed to produce dimethylpropynylidene in an argon matrix. A photochemical hydrogen shift to produce 1-penten-3-yne has been observed through infrared spectroscopy. Cyanocarbons are known to be abundant in the ISM and the atmosphere of Titan, however matrixisolation studies have not yet been carried out for a significant number of these compounds. Photolysis of 3-cyano-3-methyldiazirine should yield methylcyanocarbene, one of the simplest species in this family. Another molecule of interest is l-HC4N, which has been detected in the ISM, but has not yet been matrix-isolated and characterized. The study of arylcarbenes is vital to understanding the chemistry of carbon-rich environments, such as discharges, interstellar clouds, and circumstellar envelopes. The identification of small, sulfur containing molecules, and the identification of aromatics in the ISM make future thiophene and benzothiophene detections a real possibility. Studies on 2- and 3-diazomethyl substituted benzothiophenes are underway to assess their photochemical reactivity and potential for forming benzothiophene carbenes. Macrocylic polyynes are proposed to be involved in carbon condensation via the ring coalescence and annealing model to produce graphitic sheets or fullerenes. To simplify a complex system we are experimentally and computationally studying the series of ethynyl-substituted cyclobutadienes and their possible involvement in the build-up of larger carbon containing molecules in the ISM. The Bergman cyclization of cyclobutadiene has been explored computationally and the photochemical precursor is currently being synthesized.

Photoinactivation of Latent Herpes Simplex Virus in Rabbit Kidney Cells

PubMed Central

Kelleher, J. J.; Varani, J.

1976-01-01

The photoinactivation of actively and nonactively growing herpes simplex virus by neutral red and proflavine was studied in rabbit kidney cells. Active virus growth was inhibited by both dyes under conditions which did not destroy the cells. Neutral red caused a much greater inhibition than proflavine. Neutral red also caused a reduction in the reactivation rate of latent virus when the infected cells were treated during the latent period. In the treated cultures that did reactivate virus, the average length of the latent period was increased over the control value. Proflavine treatment did not reduce the rate of reactivation of latent virus and did not increase the average latent period of the treated cultures. PMID:185948

Adapter reagents for protein site specific dye labeling.

PubMed

Thompson, Darren A; Evans, Eric G B; Kasza, Tomas; Millhauser, Glenn L; Dawson, Philip E

2014-05-01

Chemoselective protein labeling remains a significant challenge in chemical biology. Although many selective labeling chemistries have been reported, the practicalities of matching the reaction with appropriately functionalized proteins and labeling reagents is often a challenge. For example, we encountered the challenge of site specifically labeling the cellular form of the murine Prion protein with a fluorescent dye. To facilitate this labeling, a protein was expressed with site specific p-acetylphenylalanine. However, the utility of this acetophenone reactive group is hampered by the severe lack of commercially available aminooxy fluorophores. Here we outline a general strategy for the efficient solid phase synthesis of adapter reagents capable of converting maleimido-labels into aminooxy or azide functional groups that can be further tuned for desired length or solubility properties. The utility of the adapter strategy is demonstrated in the context of fluorescent labeling of the murine Prion protein through an adapted aminooxy-Alexa dye. © 2014 Wiley Periodicals, Inc.

Adapter Reagents for Protein Site Specific Dye Labeling

PubMed Central

Thompson, Darren A.; Evans, Eric G. B.; Kasza, Tomas; Millhauser, Glenn L.; Dawson, Philip E.

2016-01-01

Chemoselective protein labeling remains a significant challenge in chemical biology. Although many selective labeling chemistries have been reported, the practicalities of matching the reaction with appropriately functionalized proteins and labeling reagents is often a challenge. For example, we encountered the challenge of site specifically labeling the cellular form of the murine Prion protein with a fluorescent dye. To facilitate this labeling, a protein was expressed with site specific p-acetylphenylalanine. However, the utility of this aceto-phenone reactive group is hampered by the severe lack of commercially available aminooxy fluorophores. Here we outline a general strategy for the efficient solid phase synthesis of adapter reagents capable of converting maleimido-labels into aminooxy or azide functional groups that can be further tuned for desired length or solubility properties. The utility of the adapter strategy is demonstrated in the context of fluorescent labeling of the murine Prion protein through an adapted aminooxy-Alexa dye. PMID:24599728

Photocatalytic Degradation Property of NANO-TiO2/DIATOMITE for Rodamine B Dye Wastewater

NASA Astrophysics Data System (ADS)

Liu, Yue; Zheng, Shuilin; Du, Gaoxiang; Shu, Feng; Chen, Juntao

The Nano-TiO2/Diatomite compound photocatalyst is used to degrade rhodamine B dye wastewater in photochemical reactor. The test result indicates that the rate of photodegradation of rhodamine B is influenced by reactive conditions. The best technical conditions are concentration of rhodamine B solution 10mg/L, ultraviolet light 300W, the compound photocatalyst amount used 1g/L, the pH 5.8, reaction time 20min. Under these conditions the rate of photodegradation of rhodamine B may reach as high as 97.80%. And the efficiency of photodegradation of catalyst only has a little changed in recycling.

A new mechanism-based inhibitor of photosynthetic water oxidation: Acetone hydrazone. I. Equilibrium reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tso, J.; Dismukes, G.C.; Petrouleas, V.

1990-08-21

The process of photosynthetic water oxidation has been investigated by using a new type of water oxidation inhibitor, the alkyl hydrazones. Acetone hydrazone (AceH), (CH{sub 3}){sub 2}CNNH{sub 2}, inhibits water oxidation by a mechanism that is analogous to that of NH{sub 2}OH. This involves binding to the water-oxidizing complex (WOC), followed by photoreversible reduction of manganese (loss of the S{sub 1} {yields} S{sub 2} reaction). At higher AceH concentrations the S{sub 1} state is reduced in the dark and Mn is released, albeit to a lesser extent than with NH{sup 2}OH. Following extraction of Mn, AceH is able to donatemore » electrons rapidly to the reaction center tyrosine radical Z{sup +} ({sup 161}Tyr-D{sub 1} protein), more slowly to a reaction center radical C{sup +}, and not at all to the dark-stable tyrosine radical D{sup +} ({sup 160}Tyr-D{sub 2} protein) which must be sequestered in an inaccessible site. Unexpectedly, Cl{sup {minus}} was found not to interfere or compete with AceH for binding to the WOC in the S{sub 1} state, in contrast to the reported rate of binding of N,N-dimethylhydroxylamine (CH{sub 3}){sub 2}NOH. The authors interpret the latter behavior as due to ionic screening of the thylakoid membrane, rather than a specific Cl site involved in water oxidation. AceH appears not to bind to the acceptor side of PSII as evidenced by normal EPR signals both for Q{sub A}{sup {minus}}Fe(II), the primary electron acceptor, and for the oxidized Fe(III) acceptor (Q{sub 400} species), in contrast to that observed with NH{sub 2}OH. AceH can be oxidized in solution by a variety of oxidants including Mn(III) to form a reactive diazo intermediate, (CH{sub 3}){sub 2}CNN, which reacts with carbonyl compounds. Oxidation to this diazo intermediate is postulated to be responsible for inhibition of the WOC.« less

Physical-chemical characterization of the textile dye Azo Ab52 degradation by corona plasma

NASA Astrophysics Data System (ADS)

Gómez, A.; Torres-Arenas, A. J.; Vergara-Sánchez, J.; Torres, C.; Reyes, P. G.; Martínez, H.; Saldarriaga-Noreña, Hugo

2017-10-01

This work characterizes the degradation of the textile dye azo Acid Black 52 by measuring several physical and chemical parameters. A corona plasma was created at atmospheric pressure and applied on the liquid-air interface of water samples containing the dye. 1.0 mM of ferrous sulfate (FeSO4) was added to 1.0 mM dye solution, for a total volume of 250 mL. For each treatment, a number of parameters were quantified. These were voltage, current, temperature, loss of volume, pH, electrical conductivity, concentration, optical mission spectra, chemical oxygen demand (COD), total organic carbon (TOC), and the removal ratio. Because of the increase in the sample temperature, the volume lost by evaporation was explored. The results show that the efficiency of the dye degradation by plasma is a function of treatment time. Moreover, the reactive concentration of FeSO4 and the exposition time of the plasma were varied at a constant volume, leading to the determination of the concentrations and optimal times. Considering the degradation and removal parameters, at the maximum treated time of 80 min, it found that COD was of 96.36%, TOC of 93.93%, and the removal ratio of 97.47%.

Optical Detection of Formaldehyde

NASA Technical Reports Server (NTRS)

Patty, Kira D.; Gregory, Don A.

2008-01-01

The potential for buildup .of formaldehyde in closed space environments poses a direct health hazard to personnel. The National Aeronautic Space Agency (NASA) has established a maximum permitted concentration of 0.04 ppm for 7 to 180 days for all space craft. Early detection is critical to ensure that formaldehyde levels do not accumulate. above these limits. New sensor technologies are needed to enable real time,in situ detection in a compact and reusable form factor. Addressing this need,research into the use of reactive fluorescent dyes which reversibly bind to formaldehyde (liquid or gas) has been conducted to support the development of a formaldehyde.sensor. In the presence of formaldehyde the dyes' characteristic fluorescence peaks shift providing the basis for an optical detection. Dye responses to formaldehyde exposure were characterized; demonstrating the optical detection of formaldehyde in under 10 seconds and down to concentrations of 0.5 ppm. To .incorporate the dye .in.an optical sensor device requires. a means of containing and manipulating the dye. Multiple form factors using two dissimilar sbstrates were considered to determine a suitable configuration. A prototype sensor was demonstrated and considerations for a field able sensor were presented. This research provides a necessary first step toward the development of a compact, reusable; real time optical formaldehyde sensor suitable for use in the U.S. space program,

The Ultrafast Wolff Rearrangement in the Gas Phase

NASA Astrophysics Data System (ADS)

Steinbacher, Andreas; Roeding, Sebastian; Brixner, Tobias; Nuernberger, Patrick

The Wolff rearrangement of gas-phase 5-diazo Meldrum's acid is disclosed with femtosecond ion spectroscopy. Distinct differences are found for 267 nm and 200 nm excitation, the latter leading to even two ultrafast rearrangement reactions.

17.9.3 Radical cations of diazo compounds

NASA Astrophysics Data System (ADS)

Davies, A. G.

This document is part of Subvolume E2 `Phosphorus-Centered Radicals, Radicals Centered on Other Heteroatoms, Organic Radical Ions' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

Stability of anti-reflection coatings via the self-assembly encapsulation of silica nanoparticles by diazo-resins

NASA Astrophysics Data System (ADS)

Metzman, Jonathan S.; Ridley, Jason I.; Khalifa, Moataz B.; Heflin, James R.

2015-12-01

A modified silica nanoparticle (MSNP) solution was formed by the encapsulation of negatively charged silica nanoparticles by the UV-crosslinkable polycation oligomer diazo-resin (DAR). Appropriate DAR encapsulation concentrations were determined by use of zeta-potential and dynamic light scattering measurements. The MSNPs were used in conjunction with poly(styrene sulfonate) (PSS) to grow homogenous ionic self-assembled multilayer anti-reflection coatings. Stability was induced within the films by the exposure of UV-irradiation that allowed for crosslinking of the DAR and PSS. The films were characterized by UV/vis/IR spectroscopy and field emission scanning electron microscopy. The transmission and reflection levels were >98.5% and <0.05%, respectively. The refractive indices resided in the 1.25-1.26 range. The solvent stability was tested by sonication of the films in a ternary solvent (H2O/DMF/ZnCl2 3:5:2 w/w/w).

Batch and Flow Photochemical Benzannulations Based on the Reaction of Ynamides and Diazo Ketones. Application to the Synthesis of Polycyclic Aromatic and Heteroaromatic Compounds

PubMed Central

Willumstad, Thomas P.; Haze, Olesya; Mak, Xiao Yin; Lam, Tin Yiu; Wang, Yu-Pu; Danheiser*, Rick L.

2013-01-01

Highly substituted polycyclic aromatic and heteroaromatic compounds are produced via a two-stage tandem benzannulation/cyclization strategy. The initial benzannulation step proceeds via a pericyclic cascade mechanism triggered by thermal or photochemical Wolff rearrangement of a diazo ketone. The photochemical process can be performed using a continuous flow reactor which facilitates carrying out reactions on a large scale and minimizes the time required for photolysis. Carbomethoxy ynamides as well as more ketenophilic bissilyl ynamines and N-sulfonyl and N-phosphoryl ynamides serve as the reaction partner in the benzannulation step. In the second stage of the strategy, RCM generates benzofused nitrogen heterocycles, and various heterocyclization processes furnish highly substituted and polycyclic indoles of types that were not available by using the previous cyclobutenone-based version of the tandem strategy. PMID:24116731

Halomonas sp. strain A55, a novel dye decolorizing bacterium from dye-uncontaminated Rift Valley Soda lake.

PubMed

Guadie, Awoke; Gessesse, Amare; Xia, Siqing

2018-04-23

Considering the saline-alkaline nature of textile wastewater and treatment requirements, microbial samples were collected from Ethiopian Rift Valley Soda Lakes. A large number of bacteria (121) were isolated from dye-uncontaminated Lakes Chitu (81.0%), Abijata (15.7%) and Arenguadie (3.3%), of which 95 isolates (78.5%) were found dye decolorizer. Many dye decolorizer from Lake Chitu positively correlated with higher pH (10.3 ± 0.1), salinity (64.6 ± 2.0%), conductivity (6.1 ± 0.3 mS cm -1 ) and Na+ (18.4 ± 0.6 g L -1 ) values observed than Abijata and Arenguadie Lakes. Through subsequent screening mechanism, strain A55 was selected to investigate the effect of nutrient (carbon and nitrogen), dissolved oxygen and dye concentration using Reactive Red 184 (RR 184). Based on morphological, biochemical and 16S rRNA gene sequence analysis, the strain was identified as Halomonas sp. Decolorization efficiencies were significantly enhanced with carbon (≥98%) and organic nitrogen (∼100%) than non-carbon/nitrogen (both<55%) supplements. Complete decolorization efficiencies were also observed under anoxic and anaerobic growth conditions. However, growing the isolate with nitrate (<30%) and aerobic (<10%) condition significantly decreased (p < 0.05) color removal efficiency. Kinetic analysis showed that pseudo-first-order best describes RR 184 decolorization process. Overall, the ability of Halomonas sp. strain A55 decolorized different dyes indicate that alkaline soda lake isolates are the potential candidate for treating color containing effluent. Copyright © 2018 Elsevier Ltd. All rights reserved.

Biodecolorization of recalcitrant dye as the sole sourceof nutrition using Curvularia clavata NZ2 and decolorization ability of its crude enzymes.

PubMed

Neoh, Chin Hong; Lam, Chi Yong; Lim, Chi Kim; Yahya, Adibah; Bay, Hui Han; Ibrahim, Zaharah; Noor, Zainura Zainon

2015-08-01

Extensive use of recalcitrant azo dyes in textile and paper industries poses a direct threat to the environment due to the carcinogenicity of their degradation products. The aim of this study was to investigate the efficiency of Curvularia clavata NZ2 in decolorization of azo dyes. The ability of the fungus to decolorize azo dyes can be evaluated as an important outcome as existing effluent treatment is unable to remove the dyes effectively. C. clavata has the ability to decolorize Reactive Black 5 (RB5), Acid Orange 7 (AO7), and Congo Red azo dyes, utilizing these as sole sources of carbon and nitrogen. Ultraviolet-visible (UV-vis) spectroscopy and Fourier infrared spectroscopy (FTIR) analysis of the extracted RB5's metabolites along with desorption tests confirmed that the decolorization process occurred due to degradation and not merely by adsorption. Enzyme activities of extracellular enzymes such as carboxymethylcellulase (CMCase), xylanase, laccase, and manganese peroxidase (MnP) were also detected during the decolorization process. Toxicity expressed as inhibition of germination was reduced significantly in fungal-treated azo dye solution when compared with the control. The cultivation of C. clavata under sequential batch system also recorded a decolorization efficiency of above 90%. The crude enzyme secreted by C. clavata also showed excellent ability to decolorize RB5 solutions with concentrations of 100 ppm (88-92%) and 1000 ppm (70-77%) without redox mediator. This proved that extracellular enzymes produced by C. clavata played a major role in decolorization of RB5.

Degradation of dye Procion Red MX-5B by electrolytic and electro-irradiated technologies using diamond electrodes.

PubMed

Cotillas, Salvador; Clematis, Davide; Cañizares, Pablo; Carpanese, Maria Paola; Rodrigo, Manuel A; Panizza, Marco

2018-05-01

This work focuses on the treatment of synthetic wastewater polluted with dye Procion Red MX-5B by different Electrochemical Advanced Oxidation Processes (EAOP) based on diamond anodes. The influence of the current density and the supporting electrolyte has been studied on dye removal and total mineralization of the organic matter. Results show that electrolysis with diamond electrodes is a suitable technology for an efficient degradation of dye. Nonetheless, the process efficiency increases when using chloride as supporting electrolyte because of the electrochemical generation of hypochlorite in wastewater which significantly contribute to dye removal. On the contrary, the total mineralization of the organic matter is more efficient in sulfate media. In this case, large amounts of peroxodisulfate are electrogenerated, favoring the complete removal of total organic carbon (TOC). On the other hand, lower current densities (10 mA cm -2 ) lead to a more efficient removal of both dye and TOC due to the mass transfer limitations of the technology. Finally, the coupling of UV light irradiation or ultrasound to electrolysis significantly improves the process performance, being photoelectrolysis the most efficient technology for the treatment of wastewater polluted with Procion Red MX-5B. This fact is due to the potential production of free chlorine or sulfate radicals that takes place by the activation of the electrogenerated oxidants. These species are more reactive than oxidants and, therefore, they quickly attack the organic matter present in wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Physicochemical modeling of reactive violet 5 dye adsorption on home-made cocoa shell and commercial activated carbons using the statistical physics theory

NASA Astrophysics Data System (ADS)

Sellaoui, Lotfi; Lima, Éder Cláudio; Dotto, Guilherme Luiz; Dias, Silvio L. P.; Ben Lamine, Abdelmottaleb

Two equilibrium models based on statistical physics, i.e., monolayer model with single energy and multilayer model with saturation, were developed and employed to access the steric and energetic aspects in the adsorption of reactive violet 5 dye (RV-5) on cocoa shell activated carbon (AC) and commercial activated carbon (CAC), at different temperatures (from 298 to 323 K). The results showed that the multilayer model with saturation was able to represent the adsorption system. This model assumes that the adsorption occurs by a formation of certain number of layers. The n values ranged from 1.10 to 2.98, indicating that the adsorbate molecules interacted in an inclined position on the adsorbent surface and aggregate in solution. The study of the total number of the formed layers (1 + L2) showed that the steric hindrance is the dominant factor. The description of the adsorbate-adsorbent interactions by calculation of the adsorption energy indicated that the process occurred by physisorption in nature, since the values were lower than 40 kJ mol-1.

Elimination of textile dyes using activated carbons prepared from vegetable residues and their characterization.

PubMed

Peláez-Cid, Alejandra-Alicia; Herrera-González, Ana-María; Salazar-Villanueva, Martín; Bautista-Hernández, Alejandro

2016-10-01

In this study, three mesoporous activated carbons prepared from vegetable residues were used to remove acid, basic, and direct dyes from aqueous solutions, and reactive and vat dyes from textile wastewater. Granular carbons obtained by chemical activation at 673 K with phosphoric acid from prickly pear peels (CarTunaQ), broccoli stems (CarBrocQ), and white sapote seeds (CarZapQ) were highly efficient for the removal of dyes. Adsorption equilibrium studies were carried out in batch systems and treated with Langmuir and Freundlich isotherms. The maximum adsorption capacities calculated from the Langmuir isotherms ranged between 131.6 and 312.5 mg/g for acid dyes, and between 277.8 and 500.0 mg/g for basic dyes at 303 K. Our objective in this paper was to show that vegetable wastes can serve as precursors for activated carbons that can be used for the adsorption of dyes. Specifically CarBrocQ was the best carbon produced for the removal of textile dyes. The color removal of dyes present in textile wastewaters was compared with that of a commercial powdered carbon, and it was found that the carbons produced using waste material reached similar efficiency levels. Carbon samples were characterized by bulk density, point of zero charge, thermogravimetric analysis, elemental analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, methylene blue adsorption isotherms at 303 K, and nitrogen adsorption isotherms at 77 K (SBET). The results show that the activated carbons possess a large specific surface area (1025-1177 m(2)/g) and high total pore volume (1.06-2.16 cm(3)/g) with average pore size diameters between 4.1 and 8.4 nm. Desorption and regeneration tests were made to test the viability of reusing the activated carbons. Copyright © 2016 Elsevier Ltd. All rights reserved.

Photochemical modification of polymeric materials and the polarization of light in ionomeric guest/host systems

NASA Astrophysics Data System (ADS)

Pan, Bo

Photochemical methods were introduced to develop important extrusion processes, through which polymers can either be functionalized or modified by altering molecular weight characteristics. Therefore, poly(methyl methacrylate) (PMMA) incorporated with a small amount of light-reactive functional groups was synthesized. These functional groups can be activated by UV irradiation in a post extrusion process to produce high molecular weight polymer and/or crosslinked polymer. Environmental stress cracking resistance of these polymers was examined and correlated to damping using dynamic mechanic analysis. To improve industrial reactive extrusion process of preparing maleic anhydride grafted polypropylene (MAR-g-PP), photografting was proposed and studied. Using benzophenone (BP) as the initiator, grafting efficiency was significantly improved compared to peroxide initiated grafting. Moreover, nearly constant conversion of maleic anhydride was observed in photografting. The high efficiency of benzophenone initiated photografting was attributed to the formation of the excited triplet state maleic anhydride. A rate constant of 6.0*109 M-1*sec-1 for the quenching of triplet state BP with MAH was obtained using laser photolysis spectroscopy. In a comparison, the hydrogen abstraction process from polypropylene by the triplet state BP molecules has a rate constant of 4.1*105 M-1*sec-1. In solution grafting with the use of benzene as the solvent, a facile triplet state energy transfer process may also occur leading to the formation of the excited triplet state MAH. Spectroscopic methods involving light were also used for the study of the guest-host interactions in polymer systems. The use of ionomers as the matrix for the oriented guest/host systems, cationic dye systems in particular, was shown to enhance polarization efficiency as well as dye uptake as comparing to conventional polymers, such as poly(vinyl alcohol). It was found that the dye molecules in carboxylated EVOH (EVOH-COONa) have higher degree of orientation than in EVOH, while polymer chain orientation is quite similar in these two polymers. The difference in the dye orientation was attributed to the ion-ion interactions between dye molecules and carboxylate groups of the modified polymer.

Detection and identification of occult HBV in blood donors in Taiwan using a commercial, multiplex, multi-dye nucleic acid amplification technology screening test.

PubMed

Lin, K T; Chang, C L; Tsai, M H; Lin, K S; Saldanha, J; Hung, C M

2014-02-01

The ability of a new generation commercial, multiplex, multi-dye test from Roche, the cobas TaqScreen MPX test, version 2.0, to detect and identify occult HBV infections was evaluated using routine donor samples from Kaohsiung Blood Bank, Taiwan. A total of 5973 samples were tested by nucleic acid amplification technology (NAT); 5898 in pools of six, 66 in pools of less than six and nine samples individually. NAT-reactive samples were retested with alternative NAT tests, and follow-up samples from the donors were tested individually by NAT and for all the HBV serological markers. Eight NAT-only-reactive donors were identified, and follow-up samples were obtained from six of the donors. The results indicated that all eight donors had an occult HBV infection with viral loads <12 IU/ml. The cobas(®) TaqScreen MPX test, version 2.0, has an advantage over the current Roche blood screening test, the cobas TaqScreen MPX test, for screening donations in countries with a high prevalence of occult HBV infections since the uncertainty associated with identifying samples with very low viremia is removed by the ability of the test to identify the viral target in samples that are reactive with the cobas TaqScreen MPX test, version 2.0. © 2013 International Society of Blood Transfusion.

Kicking the Silver Habit: Confessions of a Former Addict.

ERIC Educational Resources Information Center

Spaulding, Carl M.

1978-01-01

Reviews and compares three types of microfilm--silver halide, diazo, and vesicular. Storage and handing requirements for permanent collections are discussed, and some suggestions are offered to solve problems caused by the proliferation of nonsilver films in libraries. (MBR)

Heparin Assisted Photochemical Synthesis of Gold Nanoparticles and Their Performance as SERS Substrates

PubMed Central

Rodríguez-Torres, Maria del Pilar; Díaz-Torres, Luis Armando; Romero-Servin, Sergio

2014-01-01

Reactive and pharmaceutical-grade heparins were used as biologically compatible reducing and stabilizing agents to photochemically synthesize colloidal gold nanoparticles. Aggregates and anisotropic shapes were obtained photochemically under UV black-light lamp irradiation (λ = 366 nm). Heparin-functionalized gold nanoparticles were characterized by Scanning Electron Microscopy and UV-Vis spectroscopy. The negatively charged colloids were used for the Surface Enhanced Raman Spectroscopy (SERS) analysis of differently charged analytes (dyes). Measurements of pH were taken to inspect how the acidity of the medium affects the colloid-analyte interaction. SERS spectra were taken by mixing the dyes and the colloidal solutions without further functionalization or addition of any aggregating agent. PMID:25342319

Portable IR dye laser optofluidic microresonator as a temperature and chemical sensor.

PubMed

Lahoz, F; Martín, I R; Gil-Rostra, J; Oliva-Ramirez, M; Yubero, F; Gonzalez-Elipe, A R

2016-06-27

A compact and portable optofluidic microresonator has been fabricated and characterized. It is based on a Fabry-Perot microcavity consisting essentially of two tailored dichroic Bragg mirrors prepared by reactive magnetron sputtering deposition. The microresonator has been filled with an ethanol solution of Nile-Blue dye. Infrared laser emission has been measured with a pump threshold as low as 0.12 MW/cm² and an external energy conversion efficiency of 41%. The application of the device as a temperature and a chemical sensor is demonstrated. Small temperature variations as well as small amount of water concentrations in the liquid laser medium are detected as a shift of the resonant laser modes.

Optimization and enhancement of textile reactive Remazol black B decolorization and detoxification by environmentally isolated pH tolerant Pseudomonas aeruginosa KY284155.

PubMed

Hashem, Rasha A; Samir, Reham; Essam, Tamer M; Ali, Amal E; Amin, Magdy A

2018-05-21

Azo dyes are complex derivatives of diazene used in food and textile manufacture. They are highly recalcitrant compounds, and account for severe environmental and health problems. Different strains of Pseudomonas species were isolated from textile wastewater effluents. The bioconversion of Remazol black B (a commonly used water soluble dye) by Pseudomonas aeruginosa was observed in static conditions. The bio-decolorization process was optimized by a multi factorial Plackett-Burman experimental design. Decolorization of 200 mg L -1 reached 100% in 32 h. Interestingly, the presence of yeast extract, magnesium and iron in the culture media, highly accelerated the rate of decolorization. Moreover, one of our isolates, P. aeruginosa KY284155, was kept high degradation rates at high pH (pH = 9), which represents the pH of most textile wastewater effluents, and was able to tolerate high concentration of dye up to 500 mg L -1 . In bacteria, azo-dye degradation is often initiated by reductive azo compound cleavage catalyzed by azo-reductases. Three genes encoding azo-reductases, paazoR1, paazoR2 and paazoR3, could be identified in the genome of the isolated P. aeruginosa stain (B1). Bioinformatics analyses of the paazoR1, paazoR2 and paazoR3 genes reveal their prevalence and conservation in other P. aeruginosa strains. Chemical oxygen demand dramatically decreased and phyto-detoxification of the azo dye was accomplished by photocatalytic post treatment of the biodegradation products. We suggest applying combined biological photocatalytic post treatment for azo dyes on large scale, for effective, cheap decolorization and detoxification of azo-dyes, rendering them safe enough to be discharged in the environment.

Structure and reactivity of thiazolium azo dyes: UV-visible, resonance Raman, NMR, and computational studies of the reaction mechanism in alkaline solution.

PubMed

Abbott, Laurence C; Batchelor, Stephen N; Moore, John N

2013-03-07

UV-visible absorption, resonance Raman, and (1)H NMR spectroscopy, allied with density functional theory (DFT) calculations, have been used to study the structure, bonding, and alkaline hydrolysis mechanism of the cationic thiazloium azo dye, 2-[2-[4-(diethylamino)phenyl]diazenyl]-3-methyl-thiazolium (1a), along with a series of six related dyes with different 4-dialkylamino groups and/or other phenyl ring substituents (2a-c, 3a-c) and the related isothiazolium azo dye, 5-[2-[4-(dimethylamino)phenyl]diazenyl]-2-methyl-isothiazolium (4). These diazahemicyanine dyes are calculated to have a similar low-energy structure that is cis, trans at the (iso)thiazolium-azo group, and for which the calculated Raman spectra provide a good match with the experimental data; the calculations on these structures are used to assign and discuss the transitions giving rise to the experimental spectra, and to consider the bonding and its variation between the dyes. UV-visible, Raman, and NMR spectra recorded from minutes to several weeks after raising the pH of an aqueous solution of 1a to ca. 11.5 show that the dominant initial step in the reaction is loss of diethylamine to produce a quinonimine (ca. hours), with subsequent reactions occurring on longer time scales (ca. days to weeks); kinetic analyses give a rate constant of 2.6 × 10(-2) dm(3) mol(-1) s(-1) for reaction of 1a with OH(-). UV-visible spectra recorded on raising the pH of the other dyes in solution show similar changes that are attributed to the same general reaction mechanism, but with different rate constants for which the dependence on structure is discussed.

Interfacial polymerization for colorimetric labeling of protein expression in cells.

PubMed

Lilly, Jacob L; Sheldon, Phillip R; Hoversten, Liv J; Romero, Gabriela; Balasubramaniam, Vivek; Berron, Brad J

2014-01-01

Determining the location of rare proteins in cells typically requires the use of on-sample amplification. Antibody based recognition and enzymatic amplification is used to produce large amounts of visible label at the site of protein expression, but these techniques suffer from the presence of nonspecific reactivity in the biological sample and from poor spatial control over the label. Polymerization based amplification is a recently developed alternative means of creating an on-sample amplification for fluorescence applications, while not suffering from endogenous labels or loss of signal localization. This manuscript builds upon polymerization based amplification by developing a stable, archivable, and colorimetric mode of amplification termed Polymer Dye Labeling. The basic concept involves an interfacial polymer grown at the site of protein expression and subsequent staining of this polymer with an appropriate dye. The dyes Evans Blue and eosin were initially investigated for colorimetric response in a microarray setting, where both specifically stained polymer films on glass. The process was translated to the staining of protein expression in human dermal fibroblast cells, and Polymer Dye Labeling was specific to regions consistent with desired protein expression. The labeling is stable for over 200 days in ambient conditions and is also compatible with modern mounting medium.

Enhanced removal of azo dye using modified PAN nanofibrous membrane Fe complexes with adsorption/visible-driven photocatalysis bifunctional roles

NASA Astrophysics Data System (ADS)

Li, Fu; Dong, Yongchun; Kang, Weimin; Cheng, Bowen; Cui, Guixin

2017-05-01

A series of polyacrylonitrile (PAN) nanofibrous membrane Fe complexes as the Fenton heterogeneous catalysts were fabricated through surface modification with different ratio of hydrazine hydrate (HH) and hydroxylamine (HA) and subsequent coordination with Fe3+ ions for the synergistic removal of a typical azo dye, Reactive Red 195 (RR 195) via adsorption and visible-driven photocatalytic oxidation. Effect of molar ratio of HH and HA on surface structure characteristics of the resulting complexes were examined. Their adsorptive or photocatalytic activity was also compared by changing molar ratio of HH and HA. The results indicated that three PAN nanofibrous membrane Fe complexes prepared with simultaneous modification of HA and HH exhibited much higher adsorption and visible photocatalytic activities than the complex modified solely with HA or HH due to their distinctive surface structures containing more active sites. Their adsorption and visible photocatalytic kinetics of RR 195 followed pseudo-second-order model equation. Their high photocatalytic rate constant and large amount of dye adsorption were regarded as the main reasons for better dye removal efficiency and durability in cyclic reuse by means of the synergistic adsorption-photocatalysis process.

Comparative proteomic analysis using samples obtained with laser microdissection and saturation dye labelling.

PubMed

Wilson, Kate E; Marouga, Rita; Prime, John E; Pashby, D Paul; Orange, Paul R; Crosier, Steven; Keith, Alexander B; Lathe, Richard; Mullins, John; Estibeiro, Peter; Bergling, Helene; Hawkins, Edward; Morris, Christopher M

2005-10-01

Comparative proteomic methods are rapidly being applied to many different biological systems including complex tissues. One pitfall of these methods is that in some cases, such as oncology and neuroscience, tissue complexity requires isolation of specific cell types and sample is limited. Laser microdissection (LMD) is commonly used for obtaining such samples for proteomic studies. We have combined LMD with sensitive thiol-reactive saturation dye labelling of protein samples and 2-D DIGE to identify protein changes in a test system, the isolated CA1 pyramidal neurone layer of a transgenic (Tg) rat carrying a human amyloid precursor protein transgene. Saturation dye labelling proved to be extremely sensitive with a spot map of over 5,000 proteins being readily produced from 5 mug total protein, with over 100 proteins being significantly altered at p < 0.0005. Of the proteins identified, all showed coherent changes associated with transgene expression. It was, however, difficult to identify significantly different proteins using PMF and MALDI-TOF on gels containing less than 500 mug total protein. The use of saturation dye labelling of limiting samples will therefore require the use of highly sensitive MS techniques to identify the significantly altered proteins isolated using methods such as LMD.

Determination of the orientation of fluorescent labels relative to myosin S1 in solution from time-resolved fluorescence anisotropy experiments

NASA Astrophysics Data System (ADS)

van der Heide, Uulke A.; Gerritsen, Hans C.; Trayer, Ian P.; Levine, Yehudi K.

1992-04-01

The time-resolved fluorescence anisotropy of myosin S1 covalently labeled with Eosin-5- maleimide and 1,5-I-AEDANS was measured in solution. Each probe was specifically attached at one SH-group on the S1. The two most reactive SH sites on the heavy chain of the myosin S1 were used. The fluorescence anisotropy was measured at different excitation wavelengths. In this way, several absorption moments were utilized, each having a distinct orientation in the frame of the dye. The orientations of the transition moments in the dyes were determined in a separate experiment using an angle resolved fluorescence depolarization experiment on dyes embedded in stretched matrices of PVA polymers. The anisotropy decay curves exhibit fast (<3 ns) and slow (> 100 ns) components. The slow decay components reflect the motion of the large protein molecules. The fast anisotropy decay are attributed to a fast, but restricted, motion of the bound dye relative to the protein as experiments on free dyes in solution reveal subnanosecond anisotropy decays. The anisotropy decays have been analyzed in terms of a model which describes the restricted motion of the dye molecule relative to the protein and the overall rotation of the dye-protein complex in solution. An important element in the model is the incorporation of the orientational distribution of the dye relative to the protein. The observed anisotropy decays were analyzed using a global target approach in which the experimental data obtained at different excitation wavelengths are fitted simultaneously to the theoretical model. It is important to note that the orientational distribution of the dye relative to the protein, as well as the rotational correlation times of the motions for a dye attached to a given binding site, are independent of the excitation wavelength used. This leads to a reduction in the number of independent parameters optimized by the nonlinear least squares procedure. The orientational distribution of the dye relative to the protein obtained in this way is particularly useful for the interpretation of fluorescence depolarization data obtained from labeled muscle fibers. Indeed, knowledge of the distribution function of a dye attached to a binding site of the S1 protein is a prerequisite for a probe-independent determination of the orientational distribution of the S1 proteins themselves in the muscle fiber.

Preparation and characterization of novel PVDF nanofiltration membranes with hydrophilic property for filtration of dye aqueous solution

NASA Astrophysics Data System (ADS)

Nikooe, Naeme; Saljoughi, Ehsan

2017-08-01

In the present research, for the first time PVDF/Brij-58 blend nanofiltration membranes with remarkable performance in filtration of dye aqueous solution were prepared via immersion precipitation. A noticeable improvement in water permeation and fouling resistance of the PVDF membranes was achieved by using Brij-58 surfactant as a hydrophilic additive. Scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FT-IR) and water contact angle were applied for the investigation of membrane morphology, detection of the surface chemical composition and relative hydrophilicity/hydrophobicity, respectively. The membrane performance was studied and compared by determination of pure water flux (PWF) and filtration of synthetic reactive dye aqueous solutions as well as bovine serum albumin (BSA) as foulant model. It was found out that addition of 4 wt.% Brij-58 to the casting solution results in formation of membrane with remarkable hydrophilicity and fouling resistance (contact angle of 46° and flux recovery ratio (FRR) = 90%), higher porosity and consequently noticeable PWF (31.2 L/m2 h) and recognized dye rejection value (90%) in comparison with the pristine PVDF nanofiltration membrane. Addition of Brij-58 surfactant to the casting solution resulted in formation of NF membrane with higher hydrophilicity and permeability as well as higher dye rejection value in comparison with the addition of PEG 400 additive.

FLUX OF IONIC DYES ACROSS MICRONEEDLE-TREATED SKIN: EFFECT OF DYE MOLECULAR CHARACTERISTICS

PubMed Central

Gomaa, Yasmine A.; Garland, Martin J.; McInnes, Fiona; Donnelly, Ryan F.; El-Khordagui, Labiba K.; Wilson, Clive

2014-01-01

Drug flux across microneedle (MN)-treated skin is influenced by the characteristics of the MN array, microconduits and drug molecules in addition to the overall diffusional resistance of microconduits and viable tissue. Relative implication of these factors has not been fully explored. In the present study, the in vitro permeation of a series of six structurally related ionic xanthene dyes with different molecular weights (MW) and chemical substituents, across polymer MN-pretreated full thickness porcine skin was investigated in relation of their molecular characteristics. Phosphate buffer saline pH 7.4, the medium used in skin permeation experiments, was used to determine the equilibrium solubility of the dyes and their partition coefficient both in the isotropic n-octanol/ aqueous system and porcine skin/ aqueous system. Additionally, dissociation constants were determined potentiometrically. Results indicated that for rhodamine dyes, skin permeation of the zwitterionic form which predominates at physiological pH, was significantly reduced by an increase in MW, the presence of the chemically reactive isothiocyanate substituent reported to interact with stratum corneum proteins and the skin thickness. These factors were generally shown to override aqueous solubility, an important determinant of drug diffusion in an aqueous milieu. Findings provided more insight into the mechanism of drug permeation across MN-treated skin, of importance to both the design of MN-based transdermal drug delivery systems and in vitro skin permeation research. PMID:22960319

Adsorption of dyes using different types of clay: a review

NASA Astrophysics Data System (ADS)

Adeyemo, Aderonke Ajibola; Adeoye, Idowu Olatunbosun; Bello, Olugbenga Solomon

2017-05-01

Increasing amount of dyes in the ecosystem particularly in wastewater has propelled the search for more efficient low-cost adsorbents. The effective use of the sorption properties (high surface area and surface chemistry, lack of toxicity and potential for ion exchange) of different clays as adsorbents for the removal of different type of dyes (basic, acidic, reactive) from water and wastewater as potential alternatives to activated carbons has recently received widespread attention because of the environmental-friendly nature of clay materials. Insights into the efficiencies of raw and modified/activated clay adsorbents and ways of improving their efficiencies to obtain better results are discussed. Acid-modified clay resulted in higher rate of dye adsorption and an increased surface area and porosity (49.05 mm2 and 53.4 %). Base-modified clay has lower adsorption capacities, while ZnCl2-modified clay had the least rate of adsorption with a surface area of 44.3 mm2 and porosity of 43.4 %. This review also explores the grey areas of the adsorption properties of the raw clays and the improved performance of activated/modified clay materials with particular reference to the effects of pH, temperature, initial dye concentration and adsorbent dosage on the adsorption capacities of the clays. Various challenges encountered in using clay materials are highlighted and a number of future prospects for the adsorbents are proposed.

Plasmachemical degradation of azo dyes by humid air plasma: Yellow Supranol 4 GL, Scarlet Red Nylosan F3 GL and industrial waste.

PubMed

Abdelmalek, F; Gharbi, S; Benstaali, B; Addou, A; Brisset, J L

2004-05-01

A recent non-thermal plasma technique (i.e., a gliding arc discharge which generates reactive species at atmospheric pressure) is tested for pollution abatement of dyes dispersed in synthetic solutions and industrial effluents. Yellow Supranol 4 GL (YS) and Scarlet Red Nylosan F3 GL (SRN) are toxic synthetic dyes widely used in the Algerian textile industry and frequently present in liquid wastes of manufacture plants. Classical removal treatment processes are not efficient enough, so that the presence of dyes in liquid effluents may cause serious environmental problems, in connection with reusing waste waters for irrigation. The degradation processes achieved by the oxidising species formed in the plasma are followed by UV/VIS spectroscopy and by chemical oxygen demand measurements. They are almost complete (i.e., 92.5% for YS and 90% for dilute SRN) and rapidly follow pseudo-first-order laws, with overall estimated rate constants 3 x 10(-4) and 4 x 10(-4)s-1 for YS and SRN, respectively. The degradation rate constant for the industrial mixture (i.e., k = 1.45 x 10(-3)s-1) is a mean value for two consecutive steps (210(-3) and 6 x 10(-5)s-1) measured at the absorption peaks of the major constituent dyes, YS and SRN.

High resolution clear native electrophoresis for in-gel functional assays and fluorescence studies of membrane protein complexes.

PubMed

Wittig, Ilka; Karas, Michael; Schägger, Hermann

2007-07-01

Clear native electrophoresis and blue native electrophoresis are microscale techniques for the isolation of membrane protein complexes. The Coomassie Blue G-250 dye, used in blue native electrophoresis, interferes with in-gel fluorescence detection and in-gel catalytic activity assays. This problem can be overcome by omitting the dye in clear native electrophoresis. However, clear native electrophoresis suffers from enhanced protein aggregation and broadening of protein bands during electrophoresis and therefore has been used rarely. To preserve the advantages of both electrophoresis techniques we substituted Coomassie dye in the cathode buffer of blue native electrophoresis by non-colored mixtures of anionic and neutral detergents. Like Coomassie dye, these mixed micelles imposed a charge shift on the membrane proteins to enhance their anodic migration and improved membrane protein solubility during electrophoresis. This improved clear native electrophoresis offers a high resolution of membrane protein complexes comparable to that of blue native electrophoresis. We demonstrate the superiority of high resolution clear native electrophoresis for in-gel catalytic activity assays of mitochondrial complexes I-V. We present the first in-gel histochemical staining protocol for respiratory complex III. Moreover we demonstrate the special advantages of high resolution clear native electrophoresis for in-gel detection of fluorescent labeled proteins labeled by reactive fluorescent dyes and tagged by fluorescent proteins. The advantages of high resolution clear native electrophoresis make this technique superior for functional proteomics analyses.

Haererehalobacter sp. JS1, a bioemulsifier producing halophilic bacterium isolated from Indian solar salt works.

PubMed

Birdilla Selva Donio, Mariathason; Chelladurai Karthikeyan, Subbiahanadar; Michaelbabu, Mariavincent; Uma, Ganapathi; Raja Jeya Sekar, Ramaiyan; Citarasu, Thavasimuthu

2018-05-18

Bioemulsifier (BE)-producing Haererehalobacter sp. JS1 was isolated and identified from the solar salt works in India. The BE was extracted, purified, and characterized by Gas Chromatography-Mass Spectrometry (GC-MS) analysis. Emulsification activity was performed against different oils and dye degradation potential against different dyes. The production of BE was optimized using different carbon sources (C), nitrogen sources (N), pH, and NaCl. BE screening methods revealed that, Haererehalobacter sp. JS1 was highly positive BE production. Identification by 16S rRNA sequencing and analyses was found that, the Haererehalobacter sp. JS1 was closely related to Salinicoccus halophilus and Haererehalobacter sp. The structural characterization analysis confirmed that the partially purified bioemulsifier belongs to siloxane-type. Emulsification activity (E24) revealed that the bioemulsifier significantly (p < = 0.001) emulsified the commercial oils including coconut oil, gingelly oil, olive oil, and palmolein oils. Haererehalobacter sp. JS1 also significantly (p < = 0.001) degraded the dyes such as orange MR, direct violet, cotton red, reactive yellow, nitro green, and azo dye. RSM regression co-efficient and contour plot analysis clearly indicated that the combination of pH and NaCl helped to increase BE production. Siloxane-type of BE obtained from Haererehalobacter sp. JS1 was able to emulsify different oils and commercial dyes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The carbene insertion methodology for the catalytic functionalization of unreactive hydrocarbons: no classical C-H activation, but efficient C-H functionalization.

PubMed

Díaz-Requejo, M Mar; Belderrain, Tomás R; Nicasio, M Carmen; Pérez, Pedro J

2006-12-21

This contribution intends to highlight the use of the metal-catalyzed functionalization of unreactive carbon-hydrogen bonds by the carbene insertion methodology, that employs diazo compounds as the carbene source.