21 CFR 73.2298 - Ferric ammonium ferrocyanide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Ferric ammonium ferrocyanide. 73.2298 Section 73.2298 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL... ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the area...

Was Ferrocyanide a Prebiotic Reagent?

NASA Technical Reports Server (NTRS)

Keefe, Anthony D.; Miller, Stanley L.

1996-01-01

Hydrogen cyanide is the starting material for a diverse array of prebiotic syntheses, including those of amino acids and purines. Hydrogen cyanide also reacts with ferrous ions to give ferrocyanide, and so it is possible that ferrocyanide was common in the early ocean. This can only be true if the hydrogen cyanide concentration was high enough and the rate of reaction of cyanide with ferrous ions was fast enough. We show experimentally that the rate of formation of ferrocyanide is rapid even at low concentrations of hydrogen cyanide in the pH range 6-8, and therefore an equilibrium calculation is valid. The equilibrium concentrations of ferrocyanide are calculated as a function of hydrogen cyanide concentration, pH and temperature. The steady state concentration of hydrogen cyanide depends on the rate of synthesis by electric discharges and ultraviolet light and the rate of hydrolysis, which depends on pH and temperature. Our conclusions show that ferrocyanide was a major species in the prebiotic ocean only at the highest production rates of hydrogen cyanide in a strongly reducing atmosphere and at temperatures of 0 C or less, although small amounts would have been present at lower hydrogen cyanide production rates. The prebiotic application of ferrocyanide as a source of hydrated electrons, as a photochemical replication process, and in semi-permeable membranes is discussed.

Physical and Chemical Interactions between Mg:Al Layered Double Hydroxide and Hexacyanoferrate

NASA Astrophysics Data System (ADS)

Boclair, Joseph W.; Braterman, Paul S.; Brister, Brian D.; Wang, Zhiming; Yarberry, Faith

2001-11-01

The physical and chemical interactions of ferrocyanide (potassium and ammonium salts) and ferricyanide (potassium salt) with Mg:Al layered double hydroxides (LDH) (having Mg:Al ratios of 2 and 3) are investigated using powder XRD and FTIR spectroscopy. Physically, the potassium ferricyanide is shown to intercalate with a small local field deformation similar to that seen for hexacyanocobaltate (III) in similar materials. Chemically, the reduction of ferricyanide to ferrocyanide upon intercalation is confirmed. Physical interactions of ferrocyanide with 3:1 LDH are shown spectroscopically to include the possible generation of anions in differing environments. Chemically, ferrocyanide is shown to generate cubic ferrocyanides (of the type M2MgFe(CN)6, where M=K+ or NH+4) under conditions where free Mg2+ is likely present in solution, namely, solutions with a pH lower than ∼7.5. It is shown that the reported 2112-cm-1 band found in some chemically altered LDH ferrocyanide is indeed due to interlayer ferricyanide, but that the 2080 cm-1 band is due to the cubic material.

Respiration activity of Escherichia coli entrapped in a cone-shaped microwell and cylindrical micropore monitored by scanning electrochemical microscopy (SECM).

PubMed

Kaya, Takatoshi; Numai, Daisuke; Nagamine, Kuniaki; Aoyagi, Shigeo; Shiku, Hitoshi; Matsue, Tomokazu

2004-06-01

The metabolic activity of E. coli cells embedded in collagen gel microstructures in a cone-shaped well and in a cylindrical micropore was investigated using scanning electrochemical microscopy (SECM), based on the oxygen consumption rate and the conversion rate from ferrocyanide to ferricyanide. The analysis of the concentration profiles for oxygen and ferrocyanide afforded the oxygen consumption rate and the ferrocyanide production rate. A comparison indicated that the ferrocyanide production rates were larger than the oxygen consumption rate, and also that the rates observed in the cylindrical micropore were larger than those observed in the cone-shaped well. The ferrocyanide production rate of a single E. coli cell was calculated to be (5.4 +/- 2.6) x 10(-19) mol s(-1), using a cylindrical micropore system.

21 CFR 172.490 - Yellow prussiate of soda.

Code of Federal Regulations, 2010 CFR

2010-04-01

... soda (sodium ferrocyanide decahydrate; Na4Fe(CN)6·10H2O contains a minimum of 99 percent by weight of sodium ferrocyanide decahydrate. (b) The additive is used or intended for use as an anticaking agent in... ferrocyanide. [42 FR 14491, Mar. 15, 1977, as amended at 58 FR 17098, Apr. 1, 1993] ...

21 CFR 172.490 - Yellow prussiate of soda.

Code of Federal Regulations, 2011 CFR

2011-04-01

... soda (sodium ferrocyanide decahydrate; Na4Fe(CN)6·10H2O contains a minimum of 99 percent by weight of sodium ferrocyanide decahydrate. (b) The additive is used or intended for use as an anticaking agent in... ferrocyanide. [42 FR 14491, Mar. 15, 1977, as amended at 58 FR 17098, Apr. 1, 1993] ...

Conversion of radioactive ferrocyanide compounds to immobile glasses

DOEpatents

Schulz, Wallace W.; Dressen, A. Louise

1977-04-26

Complex radioactive ferrocyanide compounds result from the scavenging of cesium from waste products produced in the chemical reprocessing of nuclear fuel. These ferrocyanides, in accordance with this process, are converted to an immobile glass, resistant to leaching by water, by fusion together with sodium carbonate and a mixture of (a) basalt and boron trioxide (B.sub.2 O.sub.3) or (b) silica (SiO.sub.2) and lime (CaO).

Intra- and inter-atomic optical transitions of Fe, Co, and Ni ferrocyanides studied using first-principles many-electron calculations

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

Watanabe, Shinta, E-mail: s-watanabe@nucl.nagoya-u.ac.jp, E-mail: j-onoe@nucl.nagoya-u.ac.jp; Sawada, Yuki; Nakaya, Masato

We have investigated the electronic structures and optical properties of Fe, Co, and Ni ferrocyanide nanoparticles using first-principles relativistic many-electron calculations. The overall features of the theoretical absorption spectra for Fe, Ni, and Co ferrocyanides calculated using a first-principles many-electron method well reproduced the experimental one. The origins of the experimental absorption spectra were clarified by performing a configuration analysis based on the many-electron wave functions. For Fe ferrocyanide, the experimental absorption peaks originated from not only the charge-transfer transitions from Fe{sup 2+} to Fe{sup 3+} but also the 3d-3d intra-transitions of Fe{sup 3+} ions. In addition, the spin crossovermore » transition of Fe{sup 3+} predicted by the many-electron calculations was about 0.24 eV. For Co ferrocyanide, the experimental absorption peaks were mainly attributed to the 3d-3d intra-transitions of Fe{sup 2+} ions. In contrast to the Fe and Co ferrocyanides, Ni ferrocyanide showed that the absorption peaks originated from the 3d-3d intra-transitions of Ni{sup 3+} ions in a low-energy region, while from both the 3d-3d intra-transitions of Fe{sup 2+} ions and the charge-transfer transitions from Fe{sup 2+} to Ni{sup 3+} in a high-energy region. These results were quite different from those of density-functional theory (DFT) calculations. The discrepancy between the results of DFT calculations and those of many-electron calculations suggested that the intra- and inter-atomic transitions of transition metal ions are significantly affected by the many-body effects of strongly correlated 3d electrons.« less

Returning land contaminated as a result of radiation accidents to farming use.

PubMed

Voronina, A V; Blinova, M O; Semenishchev, V S; Gupta, D K

2015-06-01

An assessment is given of the possibility of sorbents based on natural aluminosilicates (glauconite and clinoptilolite) being used for remediation of radioactively contaminated land with the aim of returning it to farming use. A comparative study of selectivity and reversibility of radiocaesium and radiostrontium sorption by natural aluminosilicates as well as by modified ferrocyanide sorbents based on these aluminosilicates was made. It was found that surface modification of aluminosilicates by ferrocyanides increases the selectivity of synthesized sorbents to caesium by 100-1000 times, increases sorption capacity and makes caesium sorption almost irreversible, whereas, selectivity of these sorbents to strontium radionuclides remains approximately the same as for natural aluminosilicates. The caesium distribution coefficient for mixed nickel-potassium ferrocyanide on glauconite is 10((5.0±0.6)) L kg(-1), the static exchange capacity (SEC) is 63 mg g(-1); for mixed nickel-potassium ferrocyanide based on clinoptilolite caesium distribution coefficients in various concentration ranges are 10((7.0±1.0)), 10((5.7±0.4)) and 10((3.2±0.7)) L kg(-1), total SEC was 500 mg g(-1). Caesium leaching by various leaching solutions from saturated mixed nickel-potassium ferrocyanide based on clinoptilolite was lower than 2%; from saturated mixed nickel-potassium ferrocyanide based on glauconite it was 1.5-14.6%. Ferrocyanide sorbents, based on glauconite and clinoptilolite are recommended for remediation of land, contaminated by caesium as a result of the Fukushima accident in Japan. Use of these sorbents should decrease the transfer of caesium to agricultural vegetation up to a factor of 20. Copyright © 2015 Elsevier Ltd. All rights reserved.

21 CFR 73.2299 - Ferric ferrocyanide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a) Identity and... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

21 CFR 73.2299 - Ferric ferrocyanide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a) Identity and... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

21 CFR 73.2299 - Ferric ferrocyanide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a) Identity and... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

Leaching Characteristics of Hanford Ferrocyanide Wastes

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

Edwards, Matthew K.; Fiskum, Sandra K.; Peterson, Reid A.

2009-12-21

A series of leach tests were performed on actual Hanford Site tank wastes in support of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The samples were targeted composite slurries of high-level tank waste materials representing major complex, radioactive, tank waste mixtures at the Hanford Site. Using a filtration/leaching apparatus, sample solids were concentrated, caustic leached, and washed under conditions representative of those planned for the Pretreatment Facility in the WTP. Caustic leaching was performed to assess the mobilization of aluminum (as gibbsite, Al[OH]3, and boehmite AlO[OH]), phosphates [PO43-], chromium [Cr3+] and, to a lesser extent, oxalates [C2O42-]). Ferrocyanidemore » waste released the solid phase 137Cs during caustic leaching; this was antithetical to the other Hanford waste types studied. Previous testing on ferrocyanide tank waste focused on the aging of the ferrocyanide salt complex and its thermal compatibilities with nitrites and nitrates. Few studies, however, examined cesium mobilization in the waste. Careful consideration should be given to the pretreatment of ferrocyanide wastes in light of this new observed behavior, given the fact that previous testing on simulants indicates a vastly different cesium mobility in this waste form. The discourse of this work will address the overall ferrocyanide leaching characteristics as well as the behavior of the 137Cs during leaching.« less

21 CFR 73.2299 - Ferric ferrocyanide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Ferric ferrocyanide. 73.2299 Section 73.2299 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

21 CFR 73.2299 - Ferric ferrocyanide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Ferric ferrocyanide. 73.2299 Section 73.2299 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

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

Scheele, R.D.

In 1995, available subsegment samples of wastes taken from the Hanford Site underground radioactive waste storage tanks 241-C-112 (C-112) and 241-C-109 (C-109) were reanalyzed to determine the nickel concentrations in the samples and to determine whether the use of a nickel crucible in the analytical sample preparation biased the reported nickel concentrations reported by Simpson and coworkers and in the original report that this report supplements. The reanalysis strategy to determine nickel was to use a sodium peroxide flux in a zirconium crucible instead of the previously used potassium hydroxide flux in a nickel crucible. This supplemental report provides themore » results of the reanalyses and updates tables from the original report which reflect the new nickel analyses. Nickel is important with respect to management of the potentially reactive ferrocyanide wastes as it is one of the key defining characteristics of the solids that resulted from scavenging radiocesium using ferrocyanides. In Hanford Site wastes, few other processes introduced nickel into the wastes other than radiocobalt scavenging, which was often coupled with the ferrocyanide-scavenging process. Thus the presence of nickel in a waste provides strong evidence that the original waste was or contained ferrocyanide waste at one time. Given the potential import of nickel as a defining characteristic and marker for ferrocyanide wastes, the Pacific Northwest Laboratory`s (PNL) Analytical Chemistry Laboratory (ACL) reanalyzed available samples from tanks C-112 and C-109 using inductively coupled argon plasma/atomic emission spectrometry (ICP/AES) and an alternative sample preparation method which precluded contamination of the analytical samples with nickel.« less

Aqueous dye-sensitized solar cell electrolytes based on the ferricyanide-ferrocyanide redox couple.

PubMed

Daeneke, Torben; Uemura, Yu; Duffy, Noel W; Mozer, Attila J; Koumura, Nagatoshi; Bach, Udo; Spiccia, Leone

2012-03-02

Solar energy conversion efficiencies of over 4% have been achieved in DSCs constructed with aqueous electrolytes based on the ferricyanide-ferrocyanide redox couple, thereby avoiding the use of expensive, flammable and toxic solvents. This paradigm shift was made possible by the use of a hydrophobic organic carbazole dye. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

STRONTIUM PRECIPITATION

DOEpatents

McKenzie, T.R.

1960-09-13

A process is given for improving the precipitation of strontium from an aqueous phosphoric-acid-containing solution with nickel or cobalt ferrocyanide by simultaneously precipitating strontium or calcium phosphate. This is accomplished by adding to the ferrocyanide-containing solution calcium or strontium nitrate in a quantity to yield a concentration of from 0.004 to 0.03 and adjusting the pH of the solution to a value of above 8.

Preferential uptake of ammonium ions by zinc ferrocyanide

NASA Technical Reports Server (NTRS)

Braterman, P. S.; Arrhenius, G.; Hui, S.; Paplawsky, W.; Miller, S. L. (Principal Investigator)

1995-01-01

The concentration of ammonia from dilute aqueous solution could have facilitated many prebiotic reactions. This may be especially true if this concentration involves incorporation into an organized medium. We have shown that (unlike iron(III) ferrocyanide) zinc ferrocyanide,Zn2Fe(CN)6 xH2O, preferentially takes up ammonium ions from 0.01 M NH4Cl to give the known material Zn3(NH4)2[Fe(CN)6]2 xH2O, even in the presence of 0.01 M KCl. KCl alone gave Zn3K2[Fe(CN)6]2 xH2O. Products were characterized by elemental (CHN) analysis and powder X-ray diffraction (XRD). We attribute the remarkable specificity for the ammonium ion to the open framework of the product, which offers enough space for hydrogen-bonded ammonium ions, and infer that other inorganic materials with internal spaces rich in water may show a similar preference.

Application of Ion Exchange Technique to Decontamination of Polluted Water Generated by Fukushima Nuclear Disaster

NASA Astrophysics Data System (ADS)

Takeshita, Kenji; Ogata, Takeshi

By the Fukushima nuclear disaster, large amounts of water and sea water polluted mainly with radioactive Cs were generated and the environment around the nuclear site was contaminated by the fallout from the nuclear site. The coagulation settling process using ferric ferrocyanide and an inorganic coagulant and the adsorption process using ferric ferrocyanide granulated by silica binder were applied to the treatment of polluted water. In the coagulation settling process, Cs was removed completely from polluted water and sea water (DF∼104). In the adsorption process, the recovery of trace Cs (10 ppb) in sea water, which was not suitable for the use of zeolite, was attained successfully. Finally, the recovery of Cs from sewage sludge was tested by a combined process with the hydrothermal process using subcritical water and the coagulation settling process using ferric ferrocyanide. 96% of radioactive Cs was recovered successfully from sewage sludge with the radioactivity of 10,000 Bq/kg.

Quarterly report on Defense Nuclear Facilities Safety Board Recommendation 90-7 for the period ending December 31, 1992

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

Cash, R.J.; Dukelow, G.T.; Forbes, C.J.

1993-03-01

This is the seventh quarterly report on the progress of activities addressing safety issues associated with Hanford Site high-level radioactive waste tanks that contain ferrocyanide compounds. In the presence of oxidizing materials, such as nitrates or nitrites, ferrocyanide can be made to explode in the laboratory by heating it to high temperatures [above 285{degrees}C (545{degrees}F)]. In the mid 1950s approximately 140 metric tons of ferrocyanide were added to 24 underground high-level radioactive waste tanks. An implementation plan (Cash 1991) responding to the Defense Nuclear Facilities Safety Board Recommendation 90-7 (FR 1990) was issued in March 1991 describing the activities thatmore » were planned and underway to address each of the six parts of Recommendation 90-7. A revision to the original plan was transmitted to US Department of Energy by Westinghouse Hanford Company in December 1992. Milestones completed this quarter are described in this report. Contents of this report include: Introduction; Defense Nuclear Facilities Safety Board Implementation Plan Task Activities (Defense Nuclear Facilities Safety Board Recommendation for enhanced temperature measurement, Recommendation for continuous temperature monitoring, Recommendation for cover gas monitoring, Recommendation for ferrocyanide waste characterization, Recommendation for chemical reaction studies, and Recommendation for emergency response planning); Schedules; and References. All actions recommended by the Defense Nuclear Facilities Safety Board for emergency planning by Hanford Site emergency preparedness organizations have been completed.« less

Methods for performing electrochemical nitration reactions

DOEpatents

Lister, Tedd Edward; Fox, Robert Vincent

2010-05-11

A method for the electrochemical synthesis of dinitro compounds is disclosed. The method comprises using an anode to oxidize an inactive chemical mediator, such as a ferrocyanide (Fe(CN).sub.6.sup.-4) ion, to an active chemical mediator or oxidizing agent, such as a ferricyanide (Fe(CN).sub.6.sup.-3) ion, in the presence of a differential voltage. The oxidizing agent reacts with a nitro compound and a nitrite ion to form a geminal dinitro compound. The anode may continuously oxidize ferrocyanide to regenerate active ferricyanide, thus keeping sufficient amounts of ferricyanide available for reaction..

Efficient biodegradation of cyanide and ferrocyanide by Na-alginate beads immobilized with fungal cells of Trichoderma koningii.

PubMed

Zhou, Xiaoying; Liu, Lixing; Chen, Yunpeng; Xu, Shufa; Chen, Jie

2007-09-01

Cyanide or metal cyanide contaminations have become serious environmental and food-health problems. A fungal mutant of Trichoderma koningii, TkA8, constructed by restriction enzyme-mediated integration, has been verified to have a high cyanide degradation ability in our previous study. In this study, the mutant cells were entrapped in sodium-alginate (Na-alginate) immobilization beads to degrade cyanide and ferrocyanide in a liquid mineral medium. The results showed that the fungus in immobilization beads consisting of 3% Na-alginate and 3% CaCl2 could degrade cyanide more efficiently than a nonimmobilized fungal culture. For maximum degradation efficiency, the optimal ratio of Na-alginate and wet fungal biomass was 20:1 (m/m) and the initial pH was 6.5. In comparison, cell immobilization took at least 3 and 8 days earlier, respectively, to completely degrade cyanide and ferrocyanide. In addition, we showed that the immobilized beads could be easily recovered from the medium and reused for up to 5 batches without significant losses of fungal remediation abilities. The results of this study provide a promising alternative method for the large-scale remediation of soil or water systems from cyanide contamination.

Interim report cyanide safety studies

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

Burger, L.L.; Scheele, R.D.

1988-09-30

Over the past few years several proposals have been prepared to investigate the potential hazard of ferrocyanide-nitrate reactions that may occur in some Hanford waste tanks. In 1988 Westinghouse Hanford Company (WHC) decided to perform some of the suggested experimental work. Based on the proposal submitted in July, 1988, it was agreed to do a portion of the work during FY 1988. This report summarizes the results of that work, provides a preliminary analysis of the results, and includes recommendations for further study. The work completed consists of a brief literature search, preparation and analysis of several cesium nickel ferrocyanide,more » Cs{sub 2}NiFe(CN){sub 6}, oxdiation studies using Differential Scanning Calorimetry (DSC) and Thermogravimetry (TG), and small scale explosion tests.« less

Conversion of radioactive ferrocyanide compounds to immobile glasses

DOEpatents

Schulz, W.W.; Dressen, A.L.

1975-11-21

A method is described for converting complex radioactive ferrocyanide compounds of /sup 134/Cs and /sup 137/Cs to immobile glass that is resistant to leaching by water. The /sup 134/Cs and /sup 137/Cs are separated from nuclear waste solutions by precipitation from alkaline solutions by the addition of a soluble Ni/sup 2 +/, Zn/sup 2 +/, Cu/sup 2 +/, Co/sup 2 +/, UO/sub 2//sup 2 +/, or Mn/sup 2 +/ and K/sub 4/Fe(CN)/sub 6/. The dried, finely ground precipitate is mixed with Na/sub 2/CO/sub 3/ and a mixture of (a) basalt and B/sub 2/O/sub 3/ or (b) SiO/sub 2/ and CaO, melted, and allowed to solidify. (BLM)

Evaluation of silica/ferrocyanide composite as a dual-function material for simultaneous removal of ¹³⁷Cs⁺ and ⁹⁹TcO₄⁻ from aqueous solutions.

PubMed

Mahmoud, Mamdoh R; Seliman, Ayman F

2014-09-01

A novel mesoporous silica-coated ferrocyanide (MSCFC) composite was successfully synthesized and evaluated as a dual-function material for simultaneous removal of (137)Cs(+) cations and (99)TcO4(-) anions from aqueous solutions. Sorption behavior of both radionuclides on MSCFC under different experimental conditions has been studied using a batch technique. Results revealed that about 100% of (137)Cs(+) and 97% of (99)TcO4(-) were removed by MSCFC in the pH ranges of 2.2-12.4 and 4.1-9.5, respectively. Sorption kinetic data were analyzed by pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models, while Langmuir and Freundlich models were applied for the sorption isotherms. The maximum sorption capacity of MSCFC for radiocesium was determined and compared with other reported sorbents. Applicability of the coated ferrocyanide for simultaneous removal of (137)Cs(+) and (99)TcO4(-) from low-level liquid radioactive waste (LLLW) was also tested, and the data revealed that 99.91% and 98.34% were removed from (137)Cs(+) and (99)TcO4(-), respectively. It is concluded that MSCFC exhibits excellent efficiency for simultaneous removal of the mixed radionuclides with different charge from LLLW. Copyright © 2014 Elsevier Ltd. All rights reserved.

RECOVERY OF CESIUM FROM WASTE SOLUTIONS

DOEpatents

Burgus, W.H.

1959-06-30

This patent covers the precipitation of fission products including cesium on nickel or ferric ferrocyanide and subsequent selective dissolution from the carrier with a solution of ammonia or mercurlc nitrate.

HALE STAIN FOR SIALIC ACID-CONTAINING MUCINS. ADAPTATION TO ELECTRON MICROSCOPY.

PubMed

GASIC, G; BERWICK, L

1963-10-01

The feasibility of using the Hale stain to identify cellular sialic acid-containing mucins by electron microscopy was investigated. Three kinds of mouse ascites tumor cells were fixed in neutral buffered formalin, exposed to fresh colloidal ferric oxide, treated with potassium ferrocyanide, imbedded in Selectron, and sectioned for electron microscopy. Additional staining with uranyl acetate and potassium permanganate was done after sectioning in order to increase contrast. Those cells known to be coated with sialomucin showed deposits of electron-opaque ferric ferrocyanide crystals in the areas where sialomucin concentrations were expected. When these cells were treated with neuraminidase beforehand, these deposits did not appear. It was concluded that, with the precautions and modifications described, the Hale stain can be successfully combined with electron microscopy to identify sialomucin.

Direct Solar Charging of an Organic-Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode.

PubMed

Wedege, Kristina; Azevedo, João; Khataee, Amirreza; Bentien, Anders; Mendes, Adélio

2016-06-13

The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone-2,7-disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide-hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron-hole recombination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An uncommon case of a suicide with inhalation of hydrogen cyanide.

PubMed

Musshoff, F; Kirschbaum, K M; Madea, B

2011-01-30

An uncommon suicide by oral ingestion of potassium cyanide salts and contemporaneous inhalation of hydrogen cyanide is presented. A 48-year-old tradesman was found dead sitting in his car. A penetrating odor of bitter almonds was noticed when opening the doors. A camping stove and a cooking pot containing large amounts of dark blue crystals were found in the footwell of the car. White powder adhered to his fingers and to the area around the mouth. Furthermore bottles containing potassium ferrocyanide and different kinds of acid and leach were found in the car together with internet information about, e.g. potassium ferrocyanide and potassium cyanide. At autopsy hemorrhages and erosions of the mucosa of the respiratory tract, esophagus and stomach were found. Concentrations of cyanide were 0.2mg/l in stomach contents, 0.96mg/kg in brain tissue, 2.79mg/kg in lungs, and 5.3mg/l in blood. The white and toxic powder potassium cyanide was formed by heating of the yellow crystals of potassium ferrocyanide on the camping stove. This powder was probably ingested orally. Addition of acid converted the salt into the highly toxic gas hydrogen cyanide. Oxidation with atmospheric oxygen built the dark blue ferrous compound Prussian blue. This case report of a person who was not familiar with chemicals demonstrates the acquisition of professional information via the internet, enabling a suicide with a complex procedure. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Redox properties of the nitronyl nitroxide antioxidants studied via their reactions with nitroxyl and ferrocyanide.

PubMed

Bobko, A A; Khramtsov, V V

2015-01-01

Nitronyl nitroxides (NNs) are the paramagnetic probes that are capable of scavenging physiologically relevant reactive oxygen (ROS) and nitrogen (RNS) species, namely superoxide, nitric oxide (NO), and nitroxyl (HNO). NNs are increasingly considered as potent antioxidants and potential therapeutic agents. Understanding redox chemistry of the NNs is important for their use as antioxidants and as paramagnetic probes for discriminative detection of NO and HNO by electron paramagnetic resonance (EPR) spectroscopy. Here we investigated the redox properties of the two most commonly used NNs, including determination of the equilibrium and rate constants of their reduction by HNO and ferrocyanide, and reduction potential of the couple NN/hydroxylamine of nitronyl nitroxide (hNN). The rate constants of the reaction of the NNs with HNO were found to be equal to (1-2) × 10(4) M(-1)s(- 1) being close to the rate constants of scavenging superoxide and NO by NNs. The reduction potential of the NNs and iminonitroxides (INs, product of NNs reaction with NO) were calculated based on their reaction constants with ferrocyanide. The obtained values of the reduction potential for NN/hNN (E'0 ≈ 285 mV) and IN/hIN (E' ≈ 495 mV) are close to the corresponding values for vitamin C and vitamin E, correspondingly. The "balanced" scavenging rates of the NNs towards superoxide, NO, and HNO, and their low reduction potential being thermodynamically close to the bottom of the pecking order of oxidizing radicals, might be important factors contributing into their antioxidant activity.

Separation technique provides rapid quantitative determination of cesium-137 in irradiated nuclear fuel

NASA Technical Reports Server (NTRS)

Ellenburg, E. J.; Mc Cown, J. J.

1967-01-01

Potassium cobalt ferrocyanide is used to determine cesium-137 activity in irradiated fuel samples. It preferentially removes cesium from an acid solution of the fuel material. The residue is filtered and analyzed with a gamma spectrometer.

Chemical reactivity of nitrates and nitrites towards TBP and potassium nickel ferrocyanide between 30 and 300 deg

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

Lambertin, D.; Chartier, D.; Joussot-Dubien, C.

2007-07-01

Since the late sixties, bitumen has been widely used by the nuclear industry as a matrix for the immobilization of low- and intermediate level radioactive waste originating mainly from the nuclear activities: precipitation or evaporator concentrates, ion exchange resins, incinerator ashes, and filter materials. Depending on bitumen and operating conditions, bituminization of radioactive waste can be operated between 130 and 180 deg. C, so chemical reaction can be induced with nitrate or nitrite towards elements contained in waste (TPB, potassium nickel ferrocyanide and cobalt compound) and bitumen. These reactions are mainly exothermic this is the reason why the enthalpy reactionmore » and their temperature of initiation have to be determined independently of their concentration in waste. In this work, we have studied by Calvet Calorimetry at 0.1 deg. C/min heating rates, the behaviour of chemical elements especially oxido-reduction couples that can react at a temperature range 100- 300 deg. C (Nitrate/PPFeNi, Nitrite/PPFeNi, Nitrate/TBP, Nitrite/TBP, Nitrate/bitumen and Nitrite/bitumen). The initial temperature reaction of nitrates or nitrites towards potassium nickel ferrocyanide (PPFeNi) has been studied and is equal respectively to 225 deg. C and 175 deg. C. Because of the large scale temperature reaction of nitrate and PPFeNi, enthalpy reaction can not be calculated, although enthalpy reaction of nitrite and PPFeNi is equal to 270 kJ/mol of nitrite. Sodium Nitrate and TBP behaviour has been investigated, and an exothermic reaction at 135 deg. C until 250 deg. C is evidenced. The exothermic energy reaction is a function of TBP concentration and the enthalpy reaction has been determined. (authors)« less

The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory.

PubMed

Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara; Scheinost, Andreas; Moisy, Philippe; Petit, Sébastien; Shuh, David K; Tyliszczak, Tolek; Den Auwer, Christophe

2016-01-28

The electronic properties of actinide cations are of fundamental interest to describe intramolecular interactions and chemical bonding in the context of nuclear waste reprocessing or direct storage. The 5f and 6d orbitals are the first partially or totally vacant states in these elements, and the nature of the actinide ligand bonds is related to their ability to overlap with ligand orbitals. Because of its chemical and orbital selectivities, X-ray absorption spectroscopy (XAS) is an effective probe of actinide species frontier orbitals and for understanding actinide cation reactivity toward chelating ligands. The soft X-ray probes of the light elements provide better resolution than actinide L3-edges to obtain electronic information from the ligand. Thus coupling simulations to experimental soft X-ray spectral measurements and complementary quantum chemical calculations yields quantitative information on chemical bonding. In this study, soft X-ray XAS at the K-edges of C and N, and the L2,3-edges of Fe was used to investigate the electronic structures of the well-known ferrocyanide complexes K4Fe(II)(CN)6, thorium hexacyanoferrate Th(IV)Fe(II)(CN)6, and neodymium hexacyanoferrate KNd(III)Fe(II)(CN)6. The soft X-ray spectra were simulated based on quantum chemical calculations. Our results highlight the orbital overlapping effects and atomic effective charges in the Fe(II)(CN)6 building block. In addition to providing a detailed description of the electronic structure of the ferrocyanide complex (K4Fe(II)(CN)6), the results strongly contribute to confirming the actinide 5f and 6d orbital oddity in comparison to lanthanide 4f and 5d.

The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory

DOE PAGES

Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara; ...

2016-01-01

The electronic properties of actinide cations are of fundamental interest to describe intramolecular interactions and chemical bonding in the context of nuclear waste reprocessing or direct storage. The 5f and 6d orbitals are the first partially or totally vacant states in these elements, and the nature of the actinide ligand bonds is related to their ability to overlap with ligand orbitals. Because of its chemical and orbital selectivities, X-ray absorption spectroscopy (XAS) is an effective probe of actinide species frontier orbitals and for understanding actinide cation reactivity toward chelating ligands. The soft X-ray probes of the light elements provide bettermore » resolution than actinide L 3 -edges to obtain electronic information from the ligand. Thus coupling simulations to experimental soft X-ray spectral measurements and complementary quantum chemical calculations yields quantitative information on chemical bonding. In this study, soft X-ray XAS at the K-edges of C and N, and the L 2,3 -edges of Fe was used to investigate the electronic structures of the well-known ferrocyanide complexes K 4 Fe II (CN) 6 , thorium hexacyanoferrate Th IV Fe II (CN) 6 , and neodymium hexacyanoferrate KNd III Fe II (CN) 6 . The soft X-ray spectra were simulated based on quantum chemical calculations. Our results highlight the orbital overlapping effects and atomic effective charges in the Fe II (CN) 6 building block. In addition to providing a detailed description of the electronic structure of the ferrocyanide complex (K 4 Fe II (CN) 6 ), the results strongly contribute to confirming the actinide 5f and 6d orbital oddity in comparison to lanthanide 4f and 5d.« less

Copper Ferrocyanide Functionalized Core-Shell Magnetic Silica Composites for the Selective Removal of Cesium Ions from Radioactive Liquid Waste.

PubMed

Lee, Hyun Kyu; Yang, Da Som; Oh, Wonzin; Choi, Sang-June

2016-06-01

The copper ferrocyanide functionalized core-shell magnetic silica composite (mag@silica-CuFC) was prepared and was found to be easily separated from aqueous solutions by using magnetic field. The synthesized mag@silica-CuFC composite has a high sorption ability of Cs owing to its strong affinity for Cs as well as the high surface area of the supports. Cs sorption on the mag@silica-CuFC composite quickly reached the sorption equilibrium after 2 h of contact time. The effect of the presence of salts with a high concentration of up to 3.5 wt% on the efficiency of Cs sorption onto the composites was also studied. The maximum sorption ability was found to be maintained in the presence of up to 3.5 wt% of NaCl in the solution. Considering these results, the mag@silica-CuFC composite has great potential for use as an effective sorbent for the selective removal of radioactive Cs ions.

Redox Titration of Ferricyanide to Ferrocyanide with Ascorbic Acid: Illustrating the Nernst Equation and Beer-Lambert Law

ERIC Educational Resources Information Center

Huang, Tina H.; Salter, Gail; Kahn, Sarah L.; Gindt, Yvonne M.

2007-01-01

We have developed a simple, resilient experiment that illustrates the Nernst equation and Beer-Lambert law for our second-semester general chemistry students. In the experiment, the students monitor the reduction of ferricyanide ion, [Fe(CN)[subscript 6

The Construction and Behaviour of Ultramicroelectrodes: Investigations of Novel Electrochemical Systems.

DTIC Science & Technology

1984-11-28

equivalent circuit is simplified. Fig is an illustration of the cyclic voltametry of the ferricyanide/ferrocyanide couple at a thin ring electrode of...8217 but irreversible voltammogram for this fast redox couple at relatively low sweep speeds (2 7 ) * , *o.... 13 DISCUSSION It can be seen that the

Interactions between similar and dissimilar charged interfaces in the presence of multivalent anions.

PubMed

Moazzami-Gudarzi, Mohsen; Adam, Pavel; Smith, Alexander M; Trefalt, Gregor; Szilágyi, István; Maroni, Plinio; Borkovec, Michal

2018-04-04

Direct force measurements involving amidine latex (AL) and sulfate latex (SL) particles in aqueous solutions containing multivalent ferrocyanide anions are presented. These measurements feature three different pairs of particles, namely SL-SL, AL-SL, and AL-AL. The force profiles are quantitatively interpreted in terms of the theory by Derjaguin, Landau, Verwey, and Overbeek (DLVO) that is combined with a short-ranged exponential attraction. In monovalent salt solutions, the AL particles are positively charged, while the SL particles are negatively charged. In solutions containing ferrocyanide, the charge of the AL particles is reversed as the concentration is increased. The longer-ranged component of all force profiles is fully compatible with DLVO theory, provided effects of charge regulation are included. At shorter distances, an additional exponential attraction must be introduced, whereby the respective decay length is about 2 nm for the AL-AL pair, and below 1 nm for the SL-SL pair. This non-DLVO force is intermediate for the asymmetric AL-SL pair. These additional forces are probably related to charge fluctuations, patch-charged interactions, or hydrophobic forces.

THE LOCALIZATION OF CHOLINESTERASE ACTIVITY IN RAT CARDIAC MUSCLE BY ELECTRON MICROSCOPY

PubMed Central

Karnovsky, Morris J.

1964-01-01

A method has been developed for localizing sites of cholinesterase activity in rat cardiac muscle by electron microscopy. The method utilizes thiocholine esters as substrates, and is believed to be dependent on the reduction of ferricyanide to ferrocyanide by thiocholine released by enzymatic activity. The ferrocyanide thus formed is captured by copper to form fine, electron-opaque deposits of copper ferrocyanide, which sharply delineate sites of enzymatic activity at the ultrastructural level. Cholinesterase activity in formalin-fixed heart muscle was localized: (a) in longitudinal elements of the sarcoplasmic reticulum, but not in the T, or transverse, elements; and (b) in the A band, with virtually no activity noted in the M band, or in the H zone. The I band was also negative. No activity was detected in the sarcolemma, or in invaginations of the sarcolemma at the level of the Z band. The perinuclear element of the sarcoplasmic (endoplasmic) reticulum was frequently strongly positive. Activity at all sites was completely abolished by omitting the substrates, or by inhibition with eserine 10-4 M and diisopropylfluorophosphate 10-5 M. Eserine 10-5 M completely inhibited reaction in the sarcoplasmic reticulum, and virtually abolished that in the A band. These observations, together with the use of the relatively specific substrates and suitable controls to eliminate non-enzymatic staining, indicate that cholinesterase activity was being demonstrated. The activity in rat heart against different substrates was that of non-specific cholinesterases, in accordance with biochemical data. The activity in the A band was considered to be probably due to myosincholinesterase. It is proposed that the localization of cholinesterases in myocardium at the ultrastructural level should be taken into account in considering the possible functions of these myocardial enzymes, and it is hoped that knowledge of their localization will open up new avenues of approach in considering their physiological role in myocardium, which at present is not definitely known. PMID:14222810

Selective Capture of Cesium and Thallium from Natural Waters and Simulated Wastes with Copper Ferrocyanide Functionalized Mesoporous Silica

PubMed Central

Sangvanich, Thanapon; Sukwarotwat, Vichaya; Wiacek, Robert J.; Grudzien, Rafal M.; Fryxell, Glen E.; Addleman, R. Shane; Timchalk, Charles; Yantasee, Wassana

2010-01-01

Copper(II) ferrocyanide on mesoporous silica (FC-Cu-EDA-SAMMS™) has been evaluated against iron(III) hexacyanoferrate(II) (insoluble Prussian Blue) for removing cesium (Cs+) and thallium (Tl+) from natural waters and simulated acidic and alkaline wastes. From pH 0.1 – 7.3, FC-Cu-EDA-SAMMS had greater affinities for Cs and Tl and was less affected by the solution pH, competing cations, and matrices. SAMMS also outperformed Prussian Blue in terms of adsorption capacities (e.g., 21.7 versus 2.6 mg Cs/g in acidic waste stimulant (pH 1.1), 28.3 versus 5.8 mg Tl/g in seawater), and rate (e.g., over 95 wt% of Cs was removed from seawater after 2 min with SAMMS, while only 75 wt% was removed with Prussian Blue). SAMMS also had higher stability (e.g., 2.5 to 13-fold less Fe dissolved from 2 to 24 hr of contact time). In addition to environmental applications, SAMMS has great potential to be used as orally administered drug for limiting the absorption of radioactive Cs and toxic Tl in gastrointestinal tract. PMID:20594644

Office of River Protection Integrated Safety Management System Description

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

CLARK, D.L.

Revision O was never issued. Finding safe and environmentally sound methods of storage and disposal of 54 million gallons of highly radioactive waste contained in 177 underground tanks is the largest challenge of Hanford cleanup. TWRS was established in 1991 and continues to integrate all aspects of the treatment and management of the high-level radioactive waste tanks. In fiscal Year 1997, program objectives were advanced in a number of areas. RL TWRS refocused the program toward retrieving, treating, and immobilizing the tank wastes, while maintaining safety as first priority. Moving from a mode of storing the wastes to getting themore » waste out of the tanks will provide the greatest cleanup return on the investment and eliminate costly mortgage continuance. There were a number of safety-related achievements in FY1997. The first high priority safety issue was resolved with the removal of 16 tanks from the ''Wyden Watch List''. The list, brought forward by Senator Ron Wyden of Oregon, identified various Hanford safety issues needing attention. One of these issues was ferrocyanide, a chemical present in 24 tanks. Although ferrocyanide can ignite at high temperature, analysis found that the chemical has decomposed into harmless compounds and is no longer a concern.« less

Vertical movement of iron-cyanide complexes in soils of a former Manufactured Gas Plant site

NASA Astrophysics Data System (ADS)

Sut, Magdalena; Repmann, Frank; Raab, Thomas

2015-04-01

In Germany, soil and groundwater at more than a thousand sites are contaminated with iron-cyanide complexes. These contaminations originate from the gas purification process that was conducted in Manufactured Gas Plants (MGP). The phenomenon of iron-cyanide complexes mobility in soil, according to the literature, is mainly governed by the dissolution and precipitation of ferric ferrocyanide, which is only slightly soluble (< 1 mg L-1) under acidic conditions. This study suggests vertical transport of a colloidal ferric ferrocyanide, in the excess of iron and circum-neutral pH conditions, as an alternative process that influences the retardation of the pollutant movement through the soil profile. Preliminary in situ investigations of the two boreholes implied transport of ferric ferricyanide from the initial deposition in the wastes layer towards the sandy loam material (secondary accumulation), which possibly retarded the mobility of cyanide (CN). The acidic character of the wastes and the accumulation of the blue patches suggested the potential filter function of a sandy loam material due to colloidal transport of the ferric ferricyanide. Series of batch and column experiments, using sandy loam soil, revealed reduction of CN concentration due to mechanical filtration of precipitated solid iron-cyanide complexes and due to the formation of potassium manganese iron-cyanide (K2Mn[Fe(CN)6]).

Use of potassium ferrocyanide as habit modifier in the size reduction and phase modification of ammonium nitrate crystals in slurries.

PubMed

Vargeese, Anuj A; Joshi, Satyawati S; Krishnamurthy, V N

2010-08-15

Ammonium nitrate (AN) is an inorganic crystalline compound used as a solid propellant oxidizer and as a nitrogenous fertilizer. The practical use of AN as solid propellant oxidizer is restricted due to the near room temperature polymorphic phase transition and hygroscopicity. A good deal of effort has been expended for last many years to stabilize the polymorphic transitions of AN, so as to minimize the storage difficulties of AN based fertilizers and to achieve more environmentally benign propellant systems. Also, particles with aspect ratio nearer to one are a vital requirement in fertilizer and propellant industries. In the present study AN is crystallized in presence of trace amount of potassium ferrocyanide (K(4)Fe(CN)(6)) crystal habit modifier and kept for different time intervals. And the effect of K(4)Fe(CN)(6) on the habit and phase modification of AN was studied. Phase modified ammonium nitrate (PMAN) with a particle aspect ratio nearer to one was obtained by this method and the reasons for this modifications are discussed. The morphology changes were studied by SEM, the phase modifications were studied by DSC and the structural properties were studied by powder XRD. Copyright 2010 Elsevier B.V. All rights reserved.

Treatment of cyanide containing wastewater using cavitation based approach.

PubMed

Jawale, Rajashree H; Gogate, Parag R; Pandit, Aniruddha B

2014-07-01

Industrial wastewater streams containing high concentrations of biorefractory materials like cyanides should ideally be treated at source. In the present work, degradation of potassium ferrocyanide (K4Fe(CN)6) as a model pollutant has been investigated using cavitational reactors with possible intensification studies using different approaches. Effect of different operating parameters such as initial concentration, temperature and pH on the extent of degradation using acoustic cavitation has been investigated. For the case of hydrodynamic cavitation, flow characteristics of cavitating device (venturi) have been established initially followed by the effect of inlet pressure and pH on the extent of degradation. Under the optimized set of operating parameters, the addition of hydrogen peroxide (ratio of K4Fe(CN)6:H2O2 varied from 1:1 to 1:30 mol basis) as process intensifying approach has been investigated. The present work has conclusively established that under the set of optimized operating parameters, cavitation can be effectively used for degradation of potassium ferrocyanide. The comparative study of hydrodynamic cavitation and acoustic cavitation suggested that hydrodynamic cavitation is more energy efficient and gives higher degradation as compared to acoustic cavitation for equivalent power/energy dissipation. The present work is the first one to report comparison of cavitation based treatment schemes for degradation of cyanide containing wastewaters. Copyright © 2014 Elsevier B.V. All rights reserved.

Periodic pulses of calcium ions in a chemical system.

PubMed

Kurin-Csörgei, Krisztina; Epstein, Irving R; Orban, Miklós

2006-06-22

By coupling the bromate-sulfite-ferrocyanide oscillating chemical reaction with the complexation of calcium ion by EDTA, we construct a system that generates periodic pulses of free Ca(2+) with an amplitude of 2 orders of magnitude and a period of ca. 20 min. These pulses may be observed either with a calcium ion-selective electrode or with Arsenazo(III) as an indicator. We describe the systematic design procedure and the properties of this first abiotic calcium-based chemical oscillator.

Novel metal-filled polyimide electrodes

NASA Technical Reports Server (NTRS)

Furtsch, T. A.; Finklea, H. O.; Taylor, L. T.

1984-01-01

Palladium-coated polyimide films are evaluated as electrochemical electrodes. The film electrodes exhibit essentially identical behavior compared to bulk palladium electrodes. In aqueous 0.5M H2SO4, current peaks due to oxide formation, oxide stripping, hydrogen adsorption, and H2 oxidation are observed. The ferri/ferrocyanide redox couple is grossly irreversible in the same electrolyte. Reversible electrochemical behavior is obtained for Fe(EDTA)(1-/2-) in 1M KCl/H2O, and for ferrocene/ferricenium in 0.1M TEAP/dimethylacetamide.

Development of An Impedimetric Aptasensor for the Detection of Staphylococcus aureus.

PubMed

Reich, Peggy; Stoltenburg, Regina; Strehlitz, Beate; Frense, Dieter; Beckmann, Dieter

2017-11-21

In combination with electrochemical impedance spectroscopy, aptamer-based biosensors are a powerful tool for fast analytical devices. Herein, we present an impedimetric aptasensor for the detection of the human pathogen Staphylococcus aureus . The used aptamer targets protein A, a surface bound virulence factor of S. aureus . The thiol-modified protein A-binding aptamer was co-immobilized with 6-mercapto-1-hexanol onto gold electrodes by self-assembly. Optimization of the ratio of aptamer to 6-mercapto-1-hexanol resulted in an average density of 1.01 ± 0.44 × 10 13 aptamer molecules per cm². As shown with quartz crystal microbalance experiments, the immobilized aptamer retained its functionality to bind recombinant protein A. Our impedimetric biosensor is based on the principle that binding of target molecules to the immobilized aptamer decreases the electron transfer between electrode and ferri-/ferrocyanide in solution, which is measured as an increase of impedance. Microscale thermophoresis measurements showed that addition of the redox probe ferri-/ferrocyanide has no influence on the binding of aptamer and its target. We demonstrated that upon incubation with various concentrations of S. aureus , the charge-transfer resistance increased proportionally. The developed biosensor showed a limit of detection of 10 CFU·mL -1 and results were available within 10 minutes. The biosensor is highly selective, distinguishing non-target bacteria such as Escherichia coli and Staphylococcus epidermidis . This work highlights the immense potential of impedimetric aptasensors for future biosensing applications.

Development of An Impedimetric Aptasensor for the Detection of Staphylococcus aureus

PubMed Central

Strehlitz, Beate; Beckmann, Dieter

2017-01-01

In combination with electrochemical impedance spectroscopy, aptamer-based biosensors are a powerful tool for fast analytical devices. Herein, we present an impedimetric aptasensor for the detection of the human pathogen Staphylococcus aureus. The used aptamer targets protein A, a surface bound virulence factor of S. aureus. The thiol-modified protein A-binding aptamer was co-immobilized with 6-mercapto-1-hexanol onto gold electrodes by self-assembly. Optimization of the ratio of aptamer to 6-mercapto-1-hexanol resulted in an average density of 1.01 ± 0.44 × 1013 aptamer molecules per cm2. As shown with quartz crystal microbalance experiments, the immobilized aptamer retained its functionality to bind recombinant protein A. Our impedimetric biosensor is based on the principle that binding of target molecules to the immobilized aptamer decreases the electron transfer between electrode and ferri-/ferrocyanide in solution, which is measured as an increase of impedance. Microscale thermophoresis measurements showed that addition of the redox probe ferri-/ferrocyanide has no influence on the binding of aptamer and its target. We demonstrated that upon incubation with various concentrations of S. aureus, the charge-transfer resistance increased proportionally. The developed biosensor showed a limit of detection of 10 CFU·mL−1 and results were available within 10 minutes. The biosensor is highly selective, distinguishing non-target bacteria such as Escherichia coli and Staphylococcus epidermidis. This work highlights the immense potential of impedimetric aptasensors for future biosensing applications. PMID:29160851

Pseudo-indicator behaviour of platinum electrode explored for the potentiometric estimation of non-redox systems.

PubMed

Raashid, Syed; Chat, Oyais Ahmad; Rizvi, Masood A; Bhat, Mohsin Ahmad; Khan, Badruddin

2012-11-15

A pseudo-indicator electrode based potentiometric method for estimation of non-redox metal ions is presented. In the proposed method, nature and concentration specific impact of analyte over the redox potential of ideally polarisable Pt/pregenerated-redox-couple interface forms the basis of quantification. Utility of the method in estimation of six non-redox metal ions viz. Zn(2+), Cu(2+), Ni(2+), Cd(2+), Pb(2+), Al(3+) in the concentration range of 10(-1)-10(-3) moldm(-3), individually and as binary mixtures is also presented. Three types of potentiometric behaviours, which we ascribe to the nature specific thermodynamic and kinetic aspects of metal-EDTA binding, were observed. While Cu(2+), Ni(2+), Pb(2+) and Al(3+) were found to bind EDTA efficiently, without exchanging Fe(3+); Zn(2+) and Cd(2+) were observed to replace Fe(3+) from EDTA. In contrast, Ca(2+) and Mg(2+) were found to show no binding affinity to EDTA in the pH range employed in the present work. The proposed method was also used to explore the reversibility and the Nernestian behaviour of ferricyanide/ferrocyanide redox couple through spectroelectrochemical titration of Zn(2+) with ferrocyanide. The presented method is presaged to be a reliable and low cost future replacement for costly and delicate ion selective electrodes (ISE) in the estimation of non-redox species like Zn(2+), Cu(2+), etc. Copyright © 2012 Elsevier B.V. All rights reserved.

Direct Quantification of Cd2+ in the Presence of Cu2+ by a Combination of Anodic Stripping Voltammetry Using a Bi-Film-Modified Glassy Carbon Electrode and an Artificial Neural Network.

PubMed

Zhao, Guo; Wang, Hui; Liu, Gang

2017-07-03

Abstract : In this study, a novel method based on a Bi/glassy carbon electrode (Bi/GCE) for quantitatively and directly detecting Cd 2+ in the presence of Cu 2+ without further electrode modifications by combining square-wave anodic stripping voltammetry (SWASV) and a back-propagation artificial neural network (BP-ANN) has been proposed. The influence of the Cu 2+ concentration on the stripping response to Cd 2+ was studied. In addition, the effect of the ferrocyanide concentration on the SWASV detection of Cd 2+ in the presence of Cu 2+ was investigated. A BP-ANN with two inputs and one output was used to establish the nonlinear relationship between the concentration of Cd 2+ and the stripping peak currents of Cu 2+ and Cd 2+ . The factors affecting the SWASV detection of Cd 2+ and the key parameters of the BP-ANN were optimized. Moreover, the direct calibration model (i.e., adding 0.1 mM ferrocyanide before detection), the BP-ANN model and other prediction models were compared to verify the prediction performance of these models in terms of their mean absolute errors (MAEs), root mean square errors (RMSEs) and correlation coefficients. The BP-ANN model exhibited higher prediction accuracy than the direct calibration model and the other prediction models. Finally, the proposed method was used to detect Cd 2+ in soil samples with satisfactory results.

Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

NASA Astrophysics Data System (ADS)

Basirun, Wan J.; Sookhakian, Mehran; Baradaran, Saeid; Mahmoudian, Mohammad R.; Ebadi, Mehdi

2013-09-01

Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO.

Analytical test results for archived core composite samples from tanks 241-TY-101 and 241-TY-103

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

Beck, M.A.

1993-07-16

This report describes the analytical tests performed on archived core composite samples form a 1.085 sampling of the 241-TY-101 (101-TY) and 241-TY-103 (103-TY) single shell waste tanks. Both tanks are suspected of containing quantities of ferrocyanide compounds, as a result of process activities in the late 1950`s. Although limited quantities of the composite samples remained, attempts were made to obtain as much analytical information as possible, especially regarding the chemical and thermal properties of the material.

Content of strontium-90 and cesium-137 in a number of regions of the Baltic Sea in 1982

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

Lazarev, L.N.; Flegontov, V.M.; Gedenov, L.I.

1985-07-01

The authors present the data gathered from the samples of water and bed deposits taken at various sites in the Baltic Sea, the Gulf of Riga, and the Gulf of Finland. By means of the radiochemical method using ferrocyanide-carbonate concentration, they determine strotium-90 and cesium-137 content. The authors conclude by noting an increase in the cesium-137 content in the deep waters of the Baltic Sea and in bed deposits, and by cautioning that this development commands close attention.

Retardation of iron-cyanide complexes in the soil of a former manufactured gas plant site.

PubMed

Sut, Magdalena; Repmann, Frank; Raab, Thomas

2015-01-01

The soil in the vicinities of former Manufactured Gas Plant (MGP) sites is commonly contaminated with iron-cyanide complexes (ferric ferrocyanide). The phenomenon of cyanide mobility in soil, according to the literature, is mainly governed by the dissolution and precipitation of ferric ferrocyanide, which is only slightly soluble (<1 mg L(-1)) under acidic conditions. In this paper, retention properties of the sandy loam soil and the potential vertical movement of the solid iron-cyanide complexes, co-existing with the dissolution, sorption and precipitation reactions were investigated. Preliminary research conducted on a former MGP site implied colloidal transport of ferric ferricyanide from the initial deposition in the wastes layer towards the sandy loam material (secondary accumulation), which possibly retarded the mobility of cyanide (CN). A series of batch and column experiments were applied in order to investigate the retardation of iron-cyanide complexes by the sandy loam soil. Batch experiments revealed that in circumneutral pH conditions sandy loam material decreases the potassium ferro- and ferricyanide concentration. In column experiments a minor reduction in CN concentration was observed prior to addition of iron sulfide (FeS) layer, which induced the formation of the Prussian blue colloids in circumneutral pH conditions. Precipitated solid iron-cyanide complexes were mechanically filtered by the coherent structure of the investigated soil. Additionally, the reduction of the CN concentration of the percolation solutions by the sandy loam soil was presumably induced due to the formation of potassium manganese iron-cyanide (K2Mn[Fe(CN)6]).

Analysis report for 241-BY-104 Auger samples

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

Beck, M.A.

1994-11-10

This report describes the analysis of the surface crust samples taken from single-shell tank (SST) BY-104, suspected of containing ferrocyanide wastes. This sampling and analysis will assist in ascertaining whether there is any hazard due to combustion (burning) or explosion of these solid wastes. These characteristics are important to future efforts to characterize the salt and sludge in this type of waste tank. This report will outline the methodology and detail the results of analyses performed during the characterization of this material. All analyses were performed by Westinghouse Hanford Company at the 222-S laboratory unless stated otherwise.

An amperometric biosensor for glucose detection from glucose oxidase immobilized in polyaniline-polyvinylsulfonate-potassium ferricyanide film.

PubMed

Arslan, Fatma; Beskan, Umut

2014-08-01

In this study, a novel amperometric glucose biosensor with immobilization of glucose oxidase on electrochemically polymerized polyaniline-polyvinylsulphonate-potassium ferricyanide (Pani-Pvs-Fc) films has been accomplished via the entrapment technique. Potassium ferricyanide was used as the mediator. Determination of glucose was carried out by the oxidation of potassium ferrocyanide at 0.3 V vs. Ag/AgCl. The effects of pH and temperature were investigated, and the optimum pH value was found to be 7.5. The storage stability and the operational stability of the enzyme electrode were also studied.

Enhanced electron transfer kinetics through hybrid graphene-carbon nanotube films.

PubMed

Henry, Philémon A; Raut, Akshay S; Ubnoske, Stephen M; Parker, Charles B; Glass, Jeffrey T

2014-11-01

We report the first study of the electrochemical reactivity of a graphenated carbon nanotube (g-CNT) film. The electron transfer kinetics of the ferri-ferrocyanide couple were examined for a g-CNT film and compared to the kinetics to standard carbon nanotubes (CNTs). The g-CNT film exhibited much higher catalytic activity, with a heterogeneous electron-transfer rate constant, k 0 , approximately two orders of magnitude higher than for standard CNTs. Scanning electron microscopy and Raman spectroscopy were used to correlate the higher electron transfer kinetics with the higher edge-density of the g-CNT film.

Novel approaches based on ultrasound for treatment of wastewater containing potassium ferrocyanide.

PubMed

Jawale, Rajashree H; Tandale, Akash; Gogate, Parag R

2017-09-01

Industrial wastewaters containing biorefractory compounds like cyanide offer significant environmental problems attributed to the fact that the conventional methods have limited effectiveness and hence developing efficient treatment approaches is an important requirement. The present work investigates the use of novel treatment approach of ultrasound (US) combined with advanced oxidation techniques for the degradation of potassium ferrocyanide (KFC) for the first time. An ultrasonic bath equipped with longitudinal horn (1kW rated power and 25kHz frequency) has been used. The effect of initial pH (2-9) on the progress of degradation has been investigated initially and subsequently using the optimized pH, effect of addition of hydrogen peroxide (ratio of KFC:H 2 O 2 varied over the range of 1:0.5-1:5) and TiO 2 in the presence of H 2 O 2 (1:1 ratio by weight of TiO 2 ) as process intensifying approach has been studied. Combination of ultrasonic irradiation with ozone (O 3 ) (100-400mg/h) and ultraviolet irradiation (UV) has also been investigated. Use of combination of US with H 2 O 2, H 2 O 2 +TiO 2 and ozone resulted in extent of KFC degradation as 54.2%, 74.82% and 82.41% respectively. Combination of US with both UV and ozone was established to be the best approach yielding 92.47% degradation. The study also focused on establishing kinetic rate constants for all the treatment approaches which revealed that all the approaches followed first order kinetic mechanism with higher rate constants for the combination approaches. Overall, it has been conclusively established that ultrasound based combined treatment schemes are very effective for the treatment of KFC containing wastewaters. Copyright © 2017 Elsevier B.V. All rights reserved.

A polyamidoamine dendrimer-streptavidin supramolecular architecture for biosensor development.

PubMed

Soda, N; Arotiba, O A

2017-12-01

A novel polyamidoamine dendrimer-streptavidin supramolecular architecture suitable as a versatile platform for biosensor development is reported. The dendrimer was electrodeposited on a glassy carbon electrode via cyclic voltammetry. The dendrimer electrode was further modified with streptavidin by electrostatic attraction upon drop coating. The platform i.e. the dendrimer-streptavidin modified electrode was electrochemically interrogated in phosphate buffer, ferrocyanide and H 2 O 2 . The dendrimer-streptavidin platform was used in the preparation of a simple DNA biosensor as a proof of concept. The supramolecular architecture of dendrimer-streptavidin was stable, electroactive and thus lends itself as a versatile immobilisation layer for any biotinylated bioreceptors in biosensor development. Copyright © 2017 Elsevier B.V. All rights reserved.

Cation binding at the node of Ranvier: I. Localization of binding sites during development.

PubMed

Zagoren, J C; Raine, C S; Suzuki, K

1982-06-17

Cations are known to bind to the node of Ranvier and the paranodal regions of myelinated fibers. The integrity of these specialized structures is essential for normal conduction. Sites of cation binding can be microscopically identified by the electrondense histochemical reaction product formed by the precipitate of copper sulfate/potassium ferrocyanide. This technique was used to study the distribution of cation binding during normal development of myelinating fibers. Sciatic nerves of C57B1 mice, at 1, 3, 5, 6, 7, 8, 9, 13, 16, 18, 24 and 30 days of age, were prepared for electron microscopy following fixation in phosphate-buffered 2.5% glutaraldehyde and 1% osmic acid, microdissection and incubation in phosphate-buffered 0.1 M cupric sulfate followed by 0.1 M potassium ferrocyanide. Localization of reaction product was studied by light and electron microscopy. By light microscopy, no reaction product was observed prior to 9 days of age. At 13 days, a few nodes and paranodes exhibited reaction product. This increased in frequency and intensity up to 30 days when almost all nodes or paranodes exhibited reaction product. Ultrastructurally, diffuse reaction product was first observed at 3 days of age in the axoplasm of the node, in the paranodal extracellular space of the terminal loops, in the Schwann cell proper and in the terminal loops of Schwann cell cytoplasm. When myelinated axons fulfilled the criteria for mature nodes, reaction product was no longer observed in the Schwann cell cytoplasm, while the intensity of reaction product in the nodal axoplasm and paranodal extracellular space of the terminal loops increased. Reaction product in the latter site appeared to be interrupted by the transverse bands. These results suggest that cation binding accompanies nodal maturity and that the Schwann cell may play a role in production or storage of the cation binding substance during myelinogenesis and development.

Selective Capture of Cesium and Thallium from Natural Waters and Simulated Wastes with Copper Ferrocyanide Functionalized Mesoporous Silica

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

Sangvanich, Thanapon; Sukwarotwat, Vichaya; Wiacek, Robert J.

2010-10-15

Copper(II) ferrocyanide immobilized inside mesoporous silica MCM-41 supports (Cu-FC-EDA-SAMMSTM) has been evaluated against iron(III) hexacyanoferrate(II) (insoluble Prussian blue) for the sorption of cesium (Cs+) and thallium (Tl+) from natural waters and simulated wastes. The affinities (in term of distribution coefficients, Kd) of both sorbents for Cs and Tl were measured as a function of solution pH, competing cations, and matrices. For the entire pH studied (pH 0.1 to 7.3), Cu-FC-EDA-SAMMS had higher affinities for Cs and Tl (one to two orders of magnitude higher Kd) than Prussian blue and was less negatively impacted by the solution pH, competing cations, andmore » matrices. The adsorption isotherms and kinetics of the two sorbents for Cs and/or Tl were also determined in seawater and simulated acid and alkaline wastes. SAMMS outperformed Prussian blue in terms of maximum adsorption capacity (e.g., 21.7 versus 2.6 mg Cs/g in acid waste stimulant, pH 1.1), and rate (e.g., over 95 wt% of Cs was removed after 2 minutes with SAMMS, while only 75 wt% was removed with Prussian blue). The lower affinity, capacity, and rate of Cs and Tl sorption on Prussian blue than those on Cu-FC-EDA-SAMMS were attributed to the molecular pore sizes, which restrict mass transport, and the insoluble Cs abducts of the Prussian blue, which restrict the ability of neighboring binding sites to further bind Cs ions. On the other hand, the large pores of SAMMS not only enable faster diffusion and faster binding chemistry, but they also allow isolation of binding sites so that one Cs binding event does not impact further Cs binding. In addition, iron (Fe) dissolved from insoluble Prussian blue over 10-fold of that from Cu-FC-EDA-SAMMS after 24 hours of contact time, indicating poorer material stability of Prussian blue.« less

Evidence of the direct involvement of the substrate TCP radical in functional switching from oxyferrous O2 carrier to ferric peroxidase in the dual-function hemoglobin/dehaloperoxidase from Amphitrite ornata.

PubMed

Sun, Shengfang; Sono, Masanori; Du, Jing; Dawson, John H

2014-08-05

The coelomic O2-binding hemoglobin dehaloperoxidase (DHP) from the sea worm Amphitrite ornata is a dual-function heme protein that also possesses a peroxidase activity. Two different starting oxidation states are required for reversible O2 binding (ferrous) and peroxidase (ferric) activity, bringing into question how DHP manages the two functions. In our previous study, the copresence of substrate 2,4,6-trichlorophenol (TCP) and H2O2 was found to be essential for the conversion of oxy-DHP to enzymatically active ferric DHP. On the basis of that study, a functional switching mechanism involving substrate radicals (TCP(•)) was proposed. To further support this mechanism, herein we report details of our investigations into the H2O2-mediated conversion of oxy-DHP to the ferric or ferryl ([TCP] < [H2O2]) state triggered by both biologically relevant [TCP and 4-bromophenol (4-BP)] and nonrelevant (ferrocyanide) compounds. At <50 μM H2O2, all of these conversion reactions are completely inhibited by ferric heme ligands (KCN and imidazole), indicating the involvement of ferric DHP. Furthermore, the spin-trapping reagent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) effectively inhibits the TCP/4-BP (but not ferrocyanide)-triggered conversion of oxy-DHP to ferric DHP. These results and O2 concentration-dependent conversion rates observed in this study demonstrate that substrate TCP triggers the conversion of oxy-DHP to a peroxidase by TCP(•) oxidation of the deoxyferrous state. TCP(•) is progressively generated, by increasingly produced amounts of ferric DHP, upon H2O2 oxidation of TCP catalyzed initially by trace amounts of ferric enzyme present in the oxy-DHP sample. The data presented herein further address the mechanism of how the halophenolic substrate triggers the conversion of hemoglobin DHP into a peroxidase.

Observation of Single-Protein and DNA Macromolecule Collisions on Ultramicroelectrodes.

PubMed

Dick, Jeffrey E; Renault, Christophe; Bard, Allen J

2015-07-08

Single-molecule detection is the ultimate sensitivity in analytical chemistry and has been largely unavailable in electrochemical analysis. Here, we demonstrate the feasibility of detecting electrochemically inactive single biomacromolecules, such as enzymes, antibodies, and DNA, by blocking a solution redox reaction when molecules adsorb and block electrode sites. By oxidizing a large concentration of potassium ferrocyanide on an ultramicroelectrode (UME, radius ≤150 nm), time-resolved, discrete adsorption events of antibodies, enzymes, DNA, and polystyrene nanospheres can be differentiated from the background by their "footprint". Further, by assuming that the mass transport of proteins to the electrode surface is controlled mainly by diffusion, a size estimate using the Stokes-Einstein relationship shows good agreement of electrochemical data with known protein sizes.

Continuous-feed electrochemical cell with nonpacking particulate electrode

DOEpatents

Cooper, John F.

1995-01-01

An electrochemical cell providing full consumption of electrochemically active particles in a nonpacking, electrolyte-permeable bed has a tapered cell cavity bounded by two nonparallel surfaces separated by a distance that promotes bridging of particles across the cavity. The gap/particle size ratio is maintained as the particles are consumed, decrease in size, and travel from the point of entry to the narrower end of the cell. A cell of this configuration supports a bed of low packing density maintained in a dynamic steady state by alternate formation and collapse of particle bridges across the gap and associated voids over the entire active area of the cell. The cell design can be applied to refuelable zinc/air cells and zinc/ferrocyanide storage batteries.

Continuous-feed electrochemical cell with nonpacking particulate electrode

DOEpatents

Cooper, J.F.

1995-07-18

An electrochemical cell providing full consumption of electrochemically active particles in a nonpacking, electrolyte-permeable bed has a tapered cell cavity bounded by two nonparallel surfaces separated by a distance that promotes bridging of particles across the cavity. The gap/particle size ratio is maintained as the particles are consumed, decrease in size, and travel from the point of entry to the narrower end of the cell. A cell of this configuration supports a bed of low packing density maintained in a dynamic steady state by alternate formation and collapse of particle bridges across the gap and associated voids over the entire active area of the cell. The cell design can be applied to refuelable zinc/air cells and zinc/ferrocyanide storage batteries. 6 figs.

Direct Solar Charging of an Organic–Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode

PubMed Central

Wedege, Kristina; Azevedo, João; Khataee, Amirreza

2016-01-01

Abstract The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone‐2,7‐disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide‐hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron–hole recombination. PMID:27151516

Technology for NPP decantate treatment realized at Kola NPP

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

Stakhiv, Michael; Avezniyazov, Slava; Savkin, Alexander

2007-07-01

At Moscow SIA 'Radon' jointly with JSC 'Alliance Gamma', the technology for NPP Decantate Treatment was developed, tested and realized at Kola NPP. This technology consists of dissolving the salt residue and subsequent treatment by ozonization, separation of the deposits formed from ozonization and selective cleaning by ferro-cyanide sorbents. The nonactive salt solution goes to an industrial waste disposal site or a repository specially developed at NPP sites for 'exempt waste' products by IAEA classification. This technology was realized at Kola NPP in December 2006 year. At this time more than 1000 m{sup 3} of decantates log time stored aremore » treated. It allows solving very old problem to empty decantates' tanks at NPPs in environmentally safe manner and with high volume reduction factor. (authors)« less

Determination of 15N/14N and 13C/12C in Solid and Aqueous Cyanides

USGS Publications Warehouse

Johnson, C.A.

1996-01-01

The stable isotopic compositions of nitrogen and carbon in cyanide compounds can be determined by combusting aliquots in sealed tubes to form N2 gas and CO2 gas and analyzing the gases by mass spectrometry. Free cyanide (CN-aq + HCNaq) in simple solutions can also be analyzed by first precipitating the cyanide as copper(II) ferrocyanide and then combusting the precipitate. Reproducibility is ??0.5??? or better for both ??15N and ??13C. If empirical corrections are made on the basis of carbon yields, the reproducibility of ??13C can be improved to ??0.2???. The analytical methods described herein are sufficiently accurate and precise to apply stable isotope techniques to problems of cyanide degradation in natural waters and industrial process solutions.

Reducing Strength Prevailing at Root Surface of Plants Promotes Reduction of Ag+ and Generation of Ag0/Ag2O Nanoparticles Exogenously in Aqueous Phase

PubMed Central

Pardha-Saradhi, Peddisetty; Yamal, Gupta; Peddisetty, Tanuj; Sharmila, Peddisetty; Nagar, Shilpi; Singh, Jyoti; Nagarajan, Rajamani; Rao, Kottapalli S.

2014-01-01

Potential of root system of plants from wide range of families to effectively reduce membrane impermeable ferricyanide to ferrocyanide and blue coloured 2,6-dichlorophenol indophenol (DCPIP) to colourless DCPIPH2 both under non-sterile and sterile conditions, revealed prevalence of immense reducing strength at root surface. As generation of silver nanoparticles (NPs) from Ag+ involves reduction, present investigations were carried to evaluate if reducing strength prevailing at surface of root system can be exploited for reduction of Ag+ and exogenous generation of silver-NPs. Root system of intact plants of 16 species from 11 diverse families of angiosperms turned clear colorless AgNO3 solutions, turbid brown. Absorption spectra of these turbid brown solutions showed silver-NPs specific surface plasmon resonance peak. Transmission electron microscope coupled with energy dispersive X-ray confirmed the presence of distinct NPs in the range of 5–50 nm containing Ag. Selected area electron diffraction and powder X-ray diffraction patterns of the silver NPs showed Bragg reflections, characteristic of crystalline face-centered cubic structure of Ag0 and cubic structure of Ag2O. Root system of intact plants raised under sterile conditions also generated Ag0/Ag2O-NPs under strict sterile conditions in a manner similar to that recorded under non-sterile conditions. This revealed the inbuilt potential of root system to generate Ag0/Ag2O-NPs independent of any microorganism. Roots of intact plants reduced triphenyltetrazolium to triphenylformazon and impermeable ferricyanide to ferrocyanide, suggesting involvement of plasma membrane bound dehydrogenases in reduction of Ag+ and formation of Ag0/Ag2O-NPs. Root enzyme extract reduced triphenyltetrazolium to triphenylformazon and Ag+ to Ag0 in presence of NADH, clearly establishing potential of dehydrogenases to reduce Ag+ to Ag0, which generate Ag0/Ag2O-NPs. Findings presented in this manuscript put forth a novel, simple, economically viable and green protocol for synthesis of silver-NPs under ambient conditions in aqueous phase, using root system of intact plants. PMID:25184239

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

Varma, S.D.; Mooney, J.M.

Studies have been conducted to examine the implications of photochemical generation of O2- and its derivatization to H/sub 2/O/sub 2/ and OH in the physiology of the lens in vitro. Physiological status was determined by measuring the uptake of rubidium by the intact tissue when cultured in riboflavin-containing medium, in dark and light, and in the presence and absence of various scavengers. In the presence of light, the uptake of rubidium in the lens was greatly diminished; this suggests photodamage to the tissue. MnSOD and ferricyanide protected against this photochemical damage. The damaging process was thus initiated by the generationmore » of O2-. The tissue damage was also attenuated by catalase, ferrocyanide, and mannitol. These results, therefore, suggest the participation of hydrogen peroxide and the subsequent Haber-Weiss reaction in the photodamaging process.« less

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

Wei, Xiaoliang; Xia, Gordon; Kirby, Brent W.

Aiming to explore low-cost redox flow battery systems, a novel iron-polysulfide (Fe/S) flow battery has been demonstrated in a laboratory cell. This system employs alkali metal ferri/ferrocyanide and alkali metal polysulfides as the redox electrolytes. When proper electrodes, such as pretreated graphite felts, are used, 78% energy efficiency and 99% columbic efficiency are achieved. The remarkable advantages of this system over current state-of-the-art redox flow batteries include: 1) less corrosive and relatively environmentally benign redox solutions used; 2) excellent energy and utilization efficiencies; 3) low cost for redox electrolytes and cell components. These attributes can lead to significantly reduced capitalmore » cost and make the Fe/S flow battery system a promising low-cost energy storage technology. The major drawbacks of the present cell design are relatively low power density and possible sulfur species crossover. Further work is underway to address these concerns.« less

A biomimetic redox flow battery based on flavin mononucleotide

PubMed Central

Orita, Akihiro; Verde, Michael G.; Sakai, Masanori; Meng, Ying Shirley

2016-01-01

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures. PMID:27767026

Hydrogels Containing Prussian Blue Nanoparticles Toward Removal of Radioactive Cesium Ions.

PubMed

Kamachi, Yuichiro; Zakaria, Mohamed B; Torad, Nagy L; Nakato, Teruyuki; Ahamad, Tansir; Alshehri, Saad M; Malgras, Victor; Yamauchil, Yusuke

2016-04-01

Recent reports have demonstrated the practical application of Prussian blue (PB) nanoparticles toward environmental clean-up of radionuclide 173Cs. Herein, we prepared a large amount of PB nanoparticles by mixing both iron(III) chloride and sodium ferrocyanide hydrate as starting precursors. The obtained PB nanoparticles show a high surface area (440 m2. g-1) and consequently an excellent uptake ability of Cs ions from aqueous solutions. The uptake ability of Cs ions into poly(N-isopropylacrylamide (PNIPA) hydrogel is drastically increased up to 156.7 m2. g-1 after incorporating our PB nanoparticles, compared to 30.2 m2 . g-1 after using commercially available PB. Thus, our PB-containing PNIPA hydrogel can be considered as an excellent candidate for the removal of Cs ions from aqueous solutions, which will be useful for the remediation of the nuclear waste.

Efficient Enzyme-Free Biomimetic Sensors for Natural Phenol Detection.

PubMed

Ferreira Garcia, Luane; Ribeiro Souza, Aparecido; Sanz Lobón, Germán; Dos Santos, Wallans Torres Pio; Alecrim, Morgana Fernandes; Fontes Santiago, Mariângela; de Sotomayor, Rafael Luque Álvarez; de Souza Gil, Eric

2016-08-13

The development of sensors and biosensors based on copper enzymes and/or copper oxides for phenol sensing is disclosed in this work. The electrochemical properties were studied by cyclic and differential pulse voltammetry using standard solutions of potassium ferrocyanide, phosphate/acetate buffers and representative natural phenols in a wide pH range (3.0 to 9.0). Among the natural phenols herein investigated, the highest sensitivity was observed for rutin, a powerful antioxidant widespread in functional foods and ubiquitous in the plant kingdom. The calibration curve for rutin performed at optimum pH (7.0) was linear in a broad concentration range, 1 to 120 µM (r = 0.99), showing detection limits of 0.4 µM. The optimized biomimetic sensor was also applied in total phenol determination in natural samples, exhibiting higher stability and sensitivity as well as distinct selectivity for antioxidant compounds.

Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species

DOE PAGES

March, Anne Marie; Assefa, Tadesse A.; Bressler, Christian; ...

2015-02-09

X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (Kα and Kβ) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. Here In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES formore » time-resolved experiments. Lastly, we discuss technical improvements that will make valence-to-core XES a practical pump–probe technique.« less

Organic chemical aging mechanisms: An annotated bibliography. Waste Tank Safety Program

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

Samuels, W.D.; Camaioni, D.M.; Nelson, D.A.

1993-09-01

An annotated bibliography has been compiled of the potential chemical and radiological aging mechanisms of the organic constituents (non-ferrocyanide) that would likely be found in the UST at Hanford. The majority of the work that has been conducted on the aging of organic chemicals used for extraction and processing of nuclear materials has been in conjunction with the acid or PUREX type processes. At Hanford the waste being stored in the UST has been stabilized with caustic. The aging factors that were used in this work were radiolysis, hydrolysis and nitrite/nitrate oxidation. The purpose of this work was two-fold: tomore » determine whether or not research had been or is currently being conducted on the species associated with the Hanford UST waste, either as a mixture or as individual chemicals or chemical functionalities, and to determine what areas of chemical aging need to be addressed by further research.« less

A biomimetic redox flow battery based on flavin mononucleotide

NASA Astrophysics Data System (ADS)

Orita, Akihiro; Verde, Michael G.; Sakai, Masanori; Meng, Ying Shirley

2016-10-01

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures.

A biomimetic redox flow battery based on flavin mononucleotide.

PubMed

Orita, Akihiro; Verde, Michael G; Sakai, Masanori; Meng, Ying Shirley

2016-10-21

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures.

Facile deferration of commercial fertilizers containing iron chelates for their NMR analysis.

PubMed

Laghi, Luca; Alcañiz, Sara; Cerdán, Mar; Gomez-Gallego, Mar; Sierra, Miguel Angel; Placucci, Giuseppe; Cremonini, Mauro Andrea

2009-06-24

Ethylenediamine-N,N'-bis(o-hydroxyphenylacetic) acid (o,o-EDDHA) is widely used in commercial formulations as a Fe(3+) chelating agent to remedy iron shortage in calcareous and alkaline soils. Commercially available o,o-EDDHA-Fe(3+) formulations contain a mixture of EDDHA regioisomers (o,p-EDDHA and p,p-EDDHA), together with other, still uncharacterized, products. NMR spectroscopy can be applied to their study as long as iron is accurately removed prior to the observation. This paper shows that it is possible to obtain a deferrated solution of the organic ligands present in commercial fertilizers containing the EDDHA-Fe(3+) chelate by treating the chelate with ferrocyanide, thus forming Prussian Blue that can be easily removed by centrifugation. This iron removal process does not cause significant losses of the o,o-EDDHA ligand or its minor structural isomers.

In Vitro and In Vivo Evaluation of a Novel Ferrocyanide Functionalized Nanopourous Silica Decorporation Agent for Cesium (Cs) in Rats

PubMed Central

Timchalk, Charles; Creim, Jeffrey A; Sukwarotwat, Vichaya; Wiacek, Robert; Addleman, R Shane; Fryxell, Glen E; Yantasee, Wassana

2009-01-01

Novel decorporation agents are being developed to protect against radiological terrorist attacks. These sorbents, known as the self-assembled monolayer on mesoporous supports (SAMMS™), are hybrid materials where differing organic moieties are grafted onto mesoporous silica (SiO2). In vitro experiments focused on the evaluation, and optimization of SAMMS for capturing radiocesium (137Cs); therefore based on these studies, a ferrocyanide copper (FC-Cu-EDA)-SAMMS was advanced for in vivo evaluation. In vivo experiments were conducted comparing the performance of the SAMMS vs. insoluble Prussian blue. Groups of jugular cannulated rats (4/treatment) were evaluated. Animals in group I were administered 137Cs chloride (~40 μg/kg) by intravenous (iv) injection or oral gavage; Group II animals were administered pre-bound 137Cs- SAMMS or sequential 137Cs chloride + SAMMS (~61 ng/kg) by oral gavage; and Group III was orally administered 137Cs chloride (~61 ng/kg) followed by either 0.1 g of SAMMS or Prussian blue. Following dosing, the rats were maintained in metabolism cages for 72 hour and blood, urine and fecal samples were collected for 137Cs analysis (gamma counting). Rats were then humanely euthanized, and selected tissues analyzed. Orally administered 137Cs chloride was rapidly and well absorbed (~100% relative to iv dose), and the pharmacokinetics (blood, urine, feces & tissues) were very comparable to the iv dose group. For both exposures the urine and feces accounted for 20 and 3% of the dose, respectively. The prebound 137Cs-SAMMS was retained primarily within the feces (72% of the dose), with ~1.4% detected in the urine, suggesting that the 137Cs remained tightly bound to SAMMS. SAMMS & Prussian blue both effectively captured available 137Cs in the gut with feces accounting for 80–88% of the administered dose, while less than 2% was detected in the urine. This study suggests that the functionalized SAMMS outperforms Prussian blue in vitro at low pH, but demonstrates comparable in vivo sequestration efficacy at low exposure concentrations. The comparable response may be the result of the low 137Cs chloride dose and high sorbent dosage that was utilized. Future studies are planned to optimize SAMMS in vivo performance over a broader range of doses and conditions. PMID:20699707

In Vitro and In Vivo Evaluation of a Novel Ferrocyanide Functionalized Nanopourous Silica Decorporation Agent for Cesium in Rats

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

Timchalk, Charles; Creim, Jeffrey A.; Sukwarotwat, Vichaya

2010-09-01

Novel decorporation agents are being developed to protect against radiological terrorist attacks. These sorbents, known as the self-assembled monolayer on mesoporous supports (SAMMS™), are hybrid materials where differing organic moieties are grafted onto mesoporous silica (SiO2). In vitro experiments focused on the evaluation, and optimization of SAMMS for capturing radiocesium (137Cs); based on these studies, a ferrocyanide copper (FC-Cu-EDA)-SAMMS was advanced for in vivo evaluation. In vivo experiments were conducted comparing the performance of the SAMMS vs. insoluble Prussian blue. Groups of jugular cannulated rats (4/treatment) were evaluated. Group I was administered 137Cs (~40 μgeq/kg) by intravenous (iv) injection andmore » oral gavage; Group II was administered pre-bound 137Cs-SAMMS and sequential 137Cs + SAMMS (~61 ngeq/kg) by oral gavage; and Group III evaluated orally administered 137Cs (~0.06 μgeq/kg) followed by 0.1 g of either SAMMS or Prussian blue. Following dosing the rats were maintained in metabolism cages for 72 hour and blood, urine and fecal samples were collected for 137Cs analysis (gamma counting). Rats were then humanely euthanized, and selected tissues analyzed. Orally administered 137Cs was rapidly and well absorbed (~100% relative to iv dose), and the pharmacokinetics (blood, urine, feces & tissues) were very comparable to the iv dose group. For both exposures the urine and feces accounted for 20 and 3% of the dose, respectively. The prebound 137Cs-SAMMS was retained primarily within the feces (72% of the dose), with ~1.4% detected in the urine, suggesting that the 137Cs remained tightly bound to SAMMS. SAMMS & Prussian blue both effectively captured available 137Cs in the gut with feces accounting for 80-88% of the administered dose, while less than 2% was detected in the urine. This study suggests that the functionalized SAMMS out performs Prussian blue in vitro at low pH, but demonstrates comparable in vivo sequestration efficacy at low exposure concentrations. The comparable response may be the result of the low 137Cs dose and high sorbent dosage that was utilized. Future studies are planned to optimize SAMMS in vivo performance over a broader range of doses and conditions.« less

Excitability in chemical and biochemical pH-autocatalytic systems.

PubMed

Zagora, J; Voslar, M; Schreiberová, L; Schreiber, I

2001-01-01

Using two different kinds of pH systems--the papain catalyzed hydrolysis of N-benzoyl-L-arginine ethyl ester in a membrane reactor and the bromate-sulfite-ferrocyanide (BSF) reaction in the CSTR--we study the relation among excitability, oscillations and bistability, and the ability of the system to respond to external periodic perturbations. Excitable properties of dynamical systems are examined in terms of a threshold set which is used to characterise dynamics in the reactor subject to external periodic stimuli. A precise definition and a method of calculating the threshold set are formulated. Two kinds of excitability distinguished by either direct or indirect initiation of the activatory process are found in both pH systems. Periodic pulsed perturbations of the BSF system display a nontrivial dependence of an excitation number on the forcing period. We examined this system also in oscillatory mode by looking at the phase shifts caused by single-pulse perturbations and constructing the phase transition curves (PTCs).

Electrochemical detection of dopamine in the presence of ascorbic acid using graphene modified electrodes.

PubMed

Kim, Yang-Rae; Bong, Sungyool; Kang, Yeon-Joo; Yang, Yongtak; Mahajan, Rakesh Kumar; Kim, Jong Seung; Kim, Hasuck

2010-06-15

Dopamine plays a significant role in the function of human metabolism. It is important to develop sensitive sensor for the determination of dopamine without the interference by ascorbic acid. This paper reports the synthesis of graphene using a modified Hummer's method and its application for the electrochemical detection of dopamine. Electrochemical measurements were performed at glassy carbon electrode modified with graphene via drop-casting method. Cyclic voltammogram of ferri/ferrocyanide redox couple at graphene modified electrode showed an increased current intensity compared with glassy carbon electrode and graphite modified electrode. The decrease of charge transfer resistance was also analyzed by electrochemical impedance spectroscopy. The capacity of graphene modified electrode for selective detection of dopamine was confirmed in a sufficient amount of ascorbic acid (1 mM). The observed linear range for the determination of dopamine concentration was from 4 microM to 100 microM. The detection limit was estimated to be 2.64 microM. Copyright 2010 Elsevier B.V. All rights reserved.

Electrochemical studies of biocatalytic anode of sulfonated graphene/ferritin/glucose oxidase layer-by-layer biocomposite films for mediated electron transfer.

PubMed

Inamuddin; Haque, Sufia Ul; Naushad, Mu

2016-06-01

In this study, a bioanode was developed by using layer-by-layer (LBL) assembly of sulfonated graphene (SG)/ferritin (Frt)/glucose oxidase (GOx). The SG/Frt biocomposite was used as an electron transfer elevator and mediator, respectively. Glucose oxidase (GOx) from Aspergillus niger was applied as a glucose oxidation biocatalyst. The electrocatalytic oxidation of glucose using GOx modified electrode increases with an increase in the concentration of glucose in the range of 10-50mM. The electrochemical measurements of the electrode was carried out by using cyclic voltammetry (CV) at different scan rates (20-100mVs(-1)) in 30mM of glucose solution prepared in 0.3M potassium ferrocyanide (K4Fe(CN)6) and linear sweep voltammetry (LSV). A saturation current density of 50±2mAcm(-2) at a scan rate of 100mVs(-1) for the oxidation of 30Mm glucose is achieved. Copyright © 2016 Elsevier Inc. All rights reserved.

Hybrid bio-photo-electro-chemical cells for solar water splitting

PubMed Central

Pinhassi, Roy I.; Kallmann, Dan; Saper, Gadiel; Dotan, Hen; Linkov, Artyom; Kay, Asaf; Liveanu, Varda; Schuster, Gadi; Adir, Noam; Rothschild, Avner

2016-01-01

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm−2. Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel. PMID:27550091

Flexible Thick-Film Electrochemical Sensors: Impact of Mechanical Bending and Stress on the Electrochemical Behavior

PubMed Central

Cai, Jiaying; Cizek, Karel; Long, Brenton; McAferty, Kenyon; Campbell, Casey G.; Allee, David R.; Vogt, Bryan D.; La Belle, Jeff; Wang, Joseph

2009-01-01

The influence of the mechanical bending, rolling and crimping of flexible screen-printed electrodes upon their electrical properties and electrochemical behavior has been elucidated. Three different flexible plastic substrates, Mylar, polyethylene naphthalate (PEN), and Kapton, have been tested in connection to the printing of graphite ink working electrodes. Our data indicate that flexible printed electrodes can be bent to extremely small radii of curvature and still function well, despite a marginal increase the electrical resistance. Below critical radii of curvature of ~8 mm, full recovery of the electrical resistance occurs upon strain release. The electrochemical response is maintained for sub-mm bending radii and a 180° pinch of the electrode does not lead to device failure. The electrodes appear to be resistant to repeated bending. Such capabilities are demonstrated using model compounds, including ferrocyanide, trinitrotoluene (TNT) and nitronaphthalene (NN). These printed electrodes hold great promise for widespread applications requiring flexible, yet robust non-planar sensing devices. PMID:20160861

Hybrid micro-particles as a magnetically-guidable decontaminant for cesium-eluted ash slurry

NASA Astrophysics Data System (ADS)

Namiki, Yoshihisa; Ueyama, Toshihiko; Yoshida, Takayuki; Watanabe, Ryoei; Koido, Shigeo; Namiki, Tamami

2014-09-01

Decontamination of the radioactive cesium that is widely dispersed owing to a nuclear power station accident and concentrated in fly ash requires an effective elimination system. Radioactive fly ash contains large amounts of water-soluble cesium that can cause severe secondary contamination and represents a serious health risk, yet its complete removal is complicated and difficult. Here it is shown that a new fine-powder formulation can be magnetically guided to eliminate cesium after being mixed with the ash slurry. This formulation, termed MagCE, consists of a ferromagnetic porous structure and alkaline- and salt-resistant nickel ferrocyanide. It has potent cesium-adsorption- and magnetic-separation-properties. Because of its resistance against physical and chemical attack such as with ash particles, as well as with the high pH and salt concentration of the ash slurry, MagCE simplifies the decontamination process without the need of the continued presence of the hazardous water-soluble cesium in the treated ash.

Recent Progress in Iron-Based Electrode Materials for Grid-Scale Sodium-Ion Batteries.

PubMed

Fang, Yongjin; Chen, Zhongxue; Xiao, Lifen; Ai, Xinping; Cao, Yuliang; Yang, Hanxi

2018-03-01

Grid-scale energy storage batteries with electrode materials made from low-cost, earth-abundant elements are needed to meet the requirements of sustainable energy systems. Sodium-ion batteries (SIBs) with iron-based electrodes offer an attractive combination of low cost, plentiful structural diversity and high stability, making them ideal candidates for grid-scale energy storage systems. Although various iron-based cathode and anode materials have been synthesized and evaluated for sodium storage, further improvements are still required in terms of energy/power density and long cyclic stability for commercialization. In this Review, progress in iron-based electrode materials for SIBs, including oxides, polyanions, ferrocyanides, and sulfides, is briefly summarized. In addition, the reaction mechanisms, electrochemical performance enhancements, structure-composition-performance relationships, merits and drawbacks of iron-based electrode materials for SIBs are discussed. Such iron-based electrode materials will be competitive and attractive electrodes for next-generation energy storage devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid bio-photo-electro-chemical cells for solar water splitting.

PubMed

Pinhassi, Roy I; Kallmann, Dan; Saper, Gadiel; Dotan, Hen; Linkov, Artyom; Kay, Asaf; Liveanu, Varda; Schuster, Gadi; Adir, Noam; Rothschild, Avner

2016-08-23

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm(-2). Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel.

Toxin detection using a tyrosinase-coupled oxygen electrode.

PubMed

Smit, M H; Rechnitz, G A

1993-02-15

An enzyme-based "electrochemical canary" is described for the detection of cyanide. The sensing system imitates cyanide's site of toxicity in the mitochondria. The terminal sequence of electron transfer in aerobic respiration is mimicked by mediator coupling of tyrosinase catalysis to an electro-chemical system. An enzyme-coupled oxygen electrode is created which is sensitive to selective poisoning. Biocatalytic reduction of oxygen is promoted by electrochemically supplying tyrosinase with electrons. Thus, ferrocyanide is generated at a cathode and mediates the enzymatic reduction of oxygen to water. An enzyme-dependent reductive current can be monitored which is inhibited by cyanide in a concentration-dependent manner. Oxygen depletion in the reaction layer can be minimized by addressing enzyme activity using a potential pulsing routine. Enzyme activity is electrochemically initiated and terminated and the sensor becomes capable of continuous monitoring. Cyanide poisoning of the biological component is reversible, and it can be reused after rinsing. The resulting sensor detects cyanide based on its biological activity rather than its physical or chemical properties.

Hybrid micro-particles as a magnetically-guidable decontaminant for cesium-eluted ash slurry

PubMed Central

Namiki, Yoshihisa; Ueyama, Toshihiko; Yoshida, Takayuki; Watanabe, Ryoei; Koido, Shigeo; Namiki, Tamami

2014-01-01

Decontamination of the radioactive cesium that is widely dispersed owing to a nuclear power station accident and concentrated in fly ash requires an effective elimination system. Radioactive fly ash contains large amounts of water-soluble cesium that can cause severe secondary contamination and represents a serious health risk, yet its complete removal is complicated and difficult. Here it is shown that a new fine-powder formulation can be magnetically guided to eliminate cesium after being mixed with the ash slurry. This formulation, termed MagCE, consists of a ferromagnetic porous structure and alkaline- and salt-resistant nickel ferrocyanide. It has potent cesium-adsorption- and magnetic-separation-properties. Because of its resistance against physical and chemical attack such as with ash particles, as well as with the high pH and salt concentration of the ash slurry, MagCE simplifies the decontamination process without the need of the continued presence of the hazardous water-soluble cesium in the treated ash. PMID:25192495

Photorechargeable High Voltage Redox Battery Enabled by Ta3 N5 and GaN/Si Dual-Photoelectrode.

PubMed

Cheng, Qingmei; Fan, Weiqiang; He, Yumin; Ma, Peiyan; Vanka, Srinivas; Fan, Shizhao; Mi, Zetian; Wang, Dunwei

2017-07-01

Solar rechargeable battery combines the advantages of photoelectrochemical devices and batteries and has emerged as an attractive alternative to artificial photosynthesis for large-scale solar energy harvesting and storage. Due to the low photovoltages by the photoelectrodes, however, most previous demonstrations of unassisted photocharge have been realized on systems with low open circuit potentials (<0.8 V). In response to this critical challenge, here it is shown that the combined photovoltages exceeding 1.4 V can be obtained using a Ta 3 N 5 nanotube photoanode and a GaN nanowire/Si photocathode with high photocurrents (>5 mA cm -2 ). The photoelectrode system makes it possible to operate a 1.2 V alkaline anthraquinone/ferrocyanide redox battery with a high ideal solar-to-chemical conversion efficiency of 3.0% without externally applied potentials. Importantly, the photocharged battery is successfully discharged with a high voltage output. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid micro-particles as a magnetically-guidable decontaminant for cesium-eluted ash slurry.

PubMed

Namiki, Yoshihisa; Ueyama, Toshihiko; Yoshida, Takayuki; Watanabe, Ryoei; Koido, Shigeo; Namiki, Tamami

2014-09-05

Decontamination of the radioactive cesium that is widely dispersed owing to a nuclear power station accident and concentrated in fly ash requires an effective elimination system. Radioactive fly ash contains large amounts of water-soluble cesium that can cause severe secondary contamination and represents a serious health risk, yet its complete removal is complicated and difficult. Here it is shown that a new fine-powder formulation can be magnetically guided to eliminate cesium after being mixed with the ash slurry. This formulation, termed MagCE, consists of a ferromagnetic porous structure and alkaline- and salt-resistant nickel ferrocyanide. It has potent cesium-adsorption- and magnetic-separation-properties. Because of its resistance against physical and chemical attack such as with ash particles, as well as with the high pH and salt concentration of the ash slurry, MagCE simplifies the decontamination process without the need of the continued presence of the hazardous water-soluble cesium in the treated ash.

Effect of uniaxial stress on the electrochemical properties of graphene with point defects

NASA Astrophysics Data System (ADS)

Szroeder, Paweł; Sagalianov, Igor Yu.; Radchenko, Taras M.; Tatarenko, Valentyn A.; Prylutskyy, Yuriy I.; Strupiński, Włodzimierz

2018-06-01

We report a calculational study of electron states and the resulting electrochemical properties of uniaxially strained graphene with point defects. For this study the reduction of ferricyanide to ferrocyanide serves as a benchmark electrochemical reaction. We find that the heterogeneous electron transfer activity of the perfect graphene electrode rises under uniaxial strain. However, evolution of the cathodic reaction rate depends on the direction of strain. For moderate lattice deformations, the zigzag strain improves electrochemical performance better than the armchair strain. Standard rate constant increases by 50% at the zigzag strain of 10%. Vacancies, covalently bonded moieties, charged adatoms and substitutional impurities in the zigzag strained graphene induce changes in the shape of the curve of the cathodic reaction rate. However, this changes do not translate into the electrocatalytic activity. Vacancies and covalently bonded moieties at concentration of 0.1% do not affect the electrochemical performance. Charged adatoms and substitutional impurities give a slight increase in the standard rate constant by, respectively, 2.2% and 3.4%.

Electrochemical Activation of Diamond Microelectrodes: Implications for the In Vitro Measurement of Serotonin in the Bowel

PubMed Central

Duran, Boris; Brocenschi, Ricardo F.; France, Marion; Galligan, James J.; Swain, Greg M.

2014-01-01

The electrochemical pretreatment of diamond microelectrodes was investigated for the purpose of learning how an anodic, cathodic or a combined anodic + cathodic polarization affects the charge-transfer kinetics for two surface-sensitive redox systems: ferri/ferrocyanide and serotonin (5-hydroxytryptamine, 5-HT). The pretreatments were performed in 0.5 mol L−1 H2SO4. The anodic pretreatment was performed galvanically for 30 s at 250 mA cm−2. The 10 cathodic pretreatment was performed for 180 s at −250 mA cm−2. The combined pretreatment involved application of the anodic step first followed by the cathodic step. The results clearly demonstrate that the best performance for both redox systems is obtained after the cathodic polarization, which presumably activates the electrode by cleaning the surface and removing site-blocking surface carbon-oxygen functionalities. The cathodic pretreatment was found to be effective at activating a fouled microelectrode in situ. This observation has important implication for the measurement of 5-HT in the bowel. PMID:24802953

Development of a simple, low cost chronoamperometric assay for fructose based on a commercial graphite-nanoparticle modified screen-printed carbon electrode.

PubMed

Nicholas, Phil; Pittson, Robin; Hart, John P

2018-02-15

This paper describes the development of a simple, low cost chronoamperometric assay, for the measurement of fructose, using a graphite-nanoparticle modified screen-printed electrode (SPCE-G-COOH). Cyclic voltammetry showed that the response of the SPCE-G-COOH enhanced the sensitivity and precision, towards the enzymatically generated ferrocyanide species, over a plain SPCE; therefore the former was employed in subsequent studies. Calibration studies were carried out using chronoamperometry with a 40µl mixture containing fructose, mediator and FDH, deposited onto the SPCE-G-COOH. The response was linear from 0.1mM to 1.0mM. A commercial fruit juice sample was analysed using the developed assay and the fructose concentration was calculated to be 477mM with a precision of 3.03% (n=5). Following fortification (477mM fructose) the mean recovery was found to be 97.12% with a coefficient of variation of 6.42% (n=5); consequently, the method holds promise for the analysis of commercial fruit juices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhanced poly(L-malic acid) production from pretreated cane molasses by Aureobasidium pullulans in fed-batch fermentation.

PubMed

Xia, Jun; Xu, Jiaxing; Hu, Lei; Liu, Xiaoyan

2016-11-16

Poly(L-malic acid) (PMA) is a natural polyester with many attractive properties for biomedical application. However, the cost of PMA production is high when glucose is used as a carbon source. To solve this problem, cane molasses as a low-cost feedstock was applied for the production of PMA. Six pretreatment methods were applied to cane molasses before fermentation. Pretreatment with combined tricalcium phosphate, potassium ferrocyanide, and sulfuric acid (TPFSA) removed significant amounts of metal ions from cane molasses. The PMA concentration increased from 5.4 g/L (untreated molasses) to 36.9 g/L (TPFSA-pretreated molasses) after fermentation in shake flasks. A fed-batch fermentation strategy was then developed. In this method, TPFSA-pretreated cane molasses solution was continuously fed into the fermentor to maintain the total sugar concentration at 20 g/L. This technique generated approximately 95.4 g/L PMA with a productivity of 0.57 g/L/hr. The present study indicated that fed-batch fermentation using pretreated cane molasses is a feasible technique for producing high amounts of PMA.

Determination of precursor sites for pitting corrosion of polycrystalline titanium by using different techniques

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

Garfias-Mesias, L.F.; Alodan, M.; James, P.I.

1998-06-01

Scanning electrochemical microscopy (SECM) in ferrocyanide and bromide solutions was used to locate active sites (pitting precursors) on polycrystalline Ti where oxidation of Br{sup {minus}} and Fe(CN){sub 6}{sup 4{minus}} was possible. Analysis of the electrochemically active sites was done by using electron microscopy (SEM), energy dispersive X-ray analysis (EDX), atomic force microscopy (AFM), and in situ confocal laser scanning microscopy (CLSM). In most cases, the active sites were found to be associated with particles (inclusions) which contained mainly Al and Si; however, some other areas not associated with particles were also found to be active. Although the size of themore » inclusions was normally smaller than 20 {micro}m, as revealed by SEM and AFM imaging, in some cases larger particles were also found. Pitting corrosion tests in bromide solution at potentials above 1.5 V{sub SCE} followed by EDX analysis inside the pits and in situ CLSM observation, confirmed that most of the localized attack started in the areas where particles had been located.« less

Graphene-loaded nanofiber-modified electrodes for the ultrasensitive determination of dopamine.

PubMed

Rodthongkum, Nadnudda; Ruecha, Nipapan; Rangkupan, Ratthapol; Vachet, Richard W; Chailapakul, Orawon

2013-12-04

A novel and highly sensitive electrochemical system based on electrospun graphene/polyaniline/polystyrene (G/PANI/PS) nanofiber-modified screen-printed carbon electrodes has been developed for dopamine (DA) determination. A dramatic increase (9 times) in the current signal for the redox reaction of a standard, ferri/ferrocyanide [Fe(CN)6](3-/4-) couple was found when compared to an unmodified electrode. This modified electrode also exhibited favorable electron transfer kinetics and excellent electrocatalytic activity toward the oxidation of DA. When used together with square wave voltammetry (SWV), DA can be selectively determined in the presence of the common interferents (i.e. ascorbic acid and uric acid). Under optimal conditions, a very low limit of detection (0.05 nM) and limit of quantification (0.30 nM) were achieved for DA. In addition, a wide dynamic range of 0.1 nM to 100 μM was found for this electrode system. Finally, the system can be successfully applied to determine DA in complex biological environment (e.g. human serum, urine) with excellent reproducibility. Copyright © 2013 Elsevier B.V. All rights reserved.

Highly efficient biosensors by using well-ordered ZnO/ZnS core/shell nanotube arrays

NASA Astrophysics Data System (ADS)

Tarish, Samar; Xu, Yang; Wang, Zhijie; Mate, Faten; Al-Haddad, Ahmed; Wang, Wenxin; Lei, Yong

2017-10-01

We have studied the fabrication of highly efficient glucose sensors using well-ordered heterogeneous ZnO/ZnS core/shell nanotube arrays (CSNAs). The modified electrodes exhibit a superior electrochemical response towards ferrocyanide/ferricyanide and in glucose sensing. Further, the fabricated glucose biosensor exhibited good performance over an acceptable linear range from 2.39 × 10-5 to 2.66 × 10-4 mM, with a sensitivity of 188.34 mA mM-1 cm-2, which is higher than that of the ZnO nanotube array counterpart. A low limit of detection was realized (24 μM), which is good compared with electrodes based on conventional structures. In addition, the enhanced direct electrochemistry of glucose oxidase indicates the fast electron transfer of ZnO/ZnS CSNA electrodes, with a heterogeneous electron transfer rate constant (K s) of 1.69 s-1. The fast electron transfer is attributed to the high conductivity of the modified electrodes. The presented ZnS shell can facilitate the construction of future sensors and enhance the ZnO surface in a biological environment.

Biological Treatment of Cyanide by Using
Klebsiella pneumoniae Species

PubMed Central

Bilkay, Isil Seyis

2016-01-01

Summary In this study, optimization conditions for cyanide biodegradation by Klebsiella pneumoniae strain were determined to be 25 °C, pH=7 and 150 rpm at the concentration of 0.5 mM potassium cyanide in the medium. Additionally, it was found that K. pneumoniae strain is not only able to degrade potassium cyanide, but also to degrade potassium hexacyanoferrate(II) trihydrate and sodium ferrocyanide decahydrate with the efficiencies of 85 and 87.5%, respectively. Furthermore, this strain degraded potassium cyanide in the presence of different ions such as magnesium, nickel, cobalt, iron, chromium, arsenic and zinc, in variable concentrations (0.1, 0.25 and 0.5 mM) and as a result the amount of the bacteria in the biodegradation media decreased with the increase of ion concentration. Lastly, it was also observed that sterile crude extract of K. pneumoniae strain degraded potassium cyanide on the fifth day of incubation. Based on these results, it is concluded that both culture and sterile crude extract of K. pnemoniae will be used in cyanide removal from different wastes. PMID:28115902

A highly reversible anthraquinone-based anolyte for alkaline aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Cao, Jianyu; Tao, Meng; Chen, Hongping; Xu, Juan; Chen, Zhidong

2018-05-01

The development of electroactive organic materials for use in aqueous redox flow battery (RFB) electrolytes is highly attractive because of their structural flexibility, low cost and sustainability. Here, we report on a highly reversible anthraquinone-based anolyte (1,8-dihydroxyanthraquinone, 1,8-DHAQ) for alkaline aqueous RFB applications. Electrochemical measurements reveal the substituent position of hydroxyl groups for DHAQ isomers has a significant impact on the redox potential, electrochemical reversibility and water-solubility. 1,8-DHAQ shows the highest redox reversibility and rapidest mass diffusion among five isomeric DHAQs. The alkaline aqueous RFB using 1,8-DHAQ as the anolyte and potassium ferrocyanide as the catholyte yields open-circuit voltage approaching 1.1 V and current efficiency and capacity retention exceeding 99.3% and 99.88% per cycle, respectively. This aqueous RFB produces a maximum power density of 152 mW cm-2 at 100% SOC and 45 °C. Choline hydroxide was used as a hydrotropic agent to enhance the water-solubility of 1,8-DHAQ. 1,8-DHAQ has a maximum solubility of 3 M in 1 M KOH with 4 M choline hydroxide.

Electrochemistry in an acoustically levitated drop.

PubMed

Chainani, Edward T; Ngo, Khanh T; Scheeline, Alexander

2013-02-19

Levitated drops show potential as microreactors, especially when radicals are present as reactants or products. Solid/liquid interfaces are absent or minimized, avoiding adsorption and interfacial reaction of conventional microfluidics. We report amperometric detection in an acoustically levitated drop with simultaneous ballistic addition of reactant. A gold microelectrode sensor was fabricated with a lithographic process; active electrode area was defined by a photosensitive polyimide mask. The microdisk gold working electrode of radius 19 μm was characterized using ferrocenemethanol in aqueous buffer. Using cyclic voltammetry, the electrochemically active surface area was estimated by combining a recessed microdisk electrode model with the Randles-Sevcik equation. Computer-controlled ballistic introduction of reactant droplets into the levitated drop was developed. Chronoamperometric measurements of ferrocyanide added ballistically demonstrate electrochemical monitoring using the microfabricated electrode in a levitated drop. Although concentration increases with time due to drop evaporation, the extent of concentration is predictable with a linear evaporation model. Comparison of diffusion-limited currents in pendant and levitated drops show that convection arising from acoustic levitation causes an enhancement of diffusion-limited current on the order of 16%.

Sources and geochemical evolution of cyanide and formaldehyde

NASA Technical Reports Server (NTRS)

Arrhenius, G.

1991-01-01

The major source of cyanide has, in current paleoatmospheric models, been assumed to be the reaction of photodissociated thermospheric nitrogen with a limiting supply of stratospheric methane. Formaldehyde may be produced with more ease from an atmosphere of carbon dioxide as the dominant carbon species, and from carbonate in solution or sorbed in double layer hydroxide minerals. Potentially more important sources for cyanide and other carbon containing molecules are the partially photoprotected northern and southern auroral ovals where continuous currents reaching several mega-amperes induce ion-molecule reactions, extending into the lower stratosphere. In simulated environments of this kind, the cyanide ion is known to be produced from oxidized carbon species potentially more abundant than methane. Rainout of cyanide and formaldehyde place them in two different geochemical reaction reservoirs. In the anoxic Archean hydrosphere, about 1mM in Fe2(+), the cyanide ion would have been efficiently converted to the stable ferrocyanide complex Fe(CN) sub 6(4-), protecting it from the commonly considered fate of decomposition by hydrolysis, and eventually incorporating it in pyroaurite type minerals, most efficiently in green rust where it converts to insoluble ferriferrocyanide, prussian blue.

Biotechnological potential of Azolla filiculoides for biosorption of Cs and Sr: Application of micro-PIXE for measurement of biosorption.

PubMed

Ghorbanzadeh Mashkani, Saeid; Tajer Mohammad Ghazvini, Parisa

2009-03-01

The presence of Cs and Sr in culture medium of Azolla filiculoides caused about 27.4% and 46.3% inhibition of biomass growth, respectively, in comparison to A. filiculoides control weight which had not metals. Biosorption batch experiments were conducted to determine the Cs and Sr binding ability of native biomass and chemically modified biosorbents derived from Azolla namely ferrocyanide Azolla sorbents type 1 and type 2 (FAS1 and FAS2) and hydrogen peroxide Azolla sorbent (HAS). The best Cs and Sr removal results were obtained when A. filiculoides was treated by 2M MgCl(2) and 30ml H(2)O(2) 8mM at pH 7 for 12h and it was then washed by NaOH solution at pH 10.5 for 6h. Pretreatment of Azolla have been suggested to modify the surface characteristics which could improve biosorption process. The binding of Cs and Sr on the cell wall of Azolla was studied with micro-PIXE and FT-IR.

A magnetically drivable nanovehicle for curcumin with antioxidant capacity and MRI relaxation properties.

PubMed

Magro, Massimiliano; Campos, René; Baratella, Davide; Lima, Giuseppina; Holà, Katerina; Divoky, Clemens; Stollberger, Rudolf; Malina, Ondrej; Aparicio, Claudia; Zoppellaro, Giorgio; Zbořil, Radek; Vianello, Fabio

2014-09-08

Curcumin possesses wide-ranging anti-inflammatory and anti-cancer properties and its biological activity can be linked to its potent antioxidant capacity. Superparamagnetic maghemite (γ-Fe2 O3 ), called surface-active maghemite nanoparticles (SAMNs) were surface-modified with curcumin molecules, due to the presence of under-coordinated Fe(III) atoms on the nanoparticle surface. The so-obtained curcumin-modified SAMNs (SAMN@curcumin) had a mean size of 13±4 nm. SAMN@curcumin was characterized by transmission and scanning electron microscopy, UV/Vis, FTIR, and Mössbauer spectroscopy, X-ray powder diffraction, bulk susceptibility (SQUID), and relaxometry measurements (MRI imaging). The high negative contrast proclivity of SAMN@curcumin to act as potential contrast agent in MRI screenings was also tested. Moreover, the redox properties of bound curcumin were probed by electrochemistry. SAMN@curcumin was studied in the presence of different electroactive molecules, namely hydroquinone, NADH and ferrocyanide, to assess its redox behavior. Finally, SAMN@curcumin was electrochemically probed in the presence of hydrogen peroxide, demonstrating the stability and reactivity of bound curcumin. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Demetalation of Fe, Mn, and Cu chelates and complexes: application to the NMR analysis of micronutrient fertilizers.

PubMed

López-Rayo, Sandra; Lucena, Juan J; Laghi, Luca; Cremonini, Mauro A

2011-12-28

The application of nuclear magnetic resonance (NMR) for the quality control of fertilizers based on Fe(3+), Mn(2+), and Cu(2+) chelates and complexes is precluded by the strong paramagnetism of metals. Recently, a method based on the use of ferrocyanide has been described to remove iron from commercial iron chelates based on the o,o-EDDHA [ethylenediamine-N,N'bis(2-hydroxyphenylacetic)acid] chelating agent for their analysis and quantification by NMR. The present work extended that procedure to other paramagnetic ions, manganese and copper, and other chelating, EDTA (ethylenediaminetetraacetic acid), IDHA [N-(1,2-dicarboxyethyl)-d,l-aspartic acid], and complexing agents, gluconate and heptagluconate. Results showed that the removal of the paramagnetic ions was complete, allowing us to obtain (1)H NMR spectra characterized by narrow peaks. The quantification of the ligands by NMR and high-performance liquid chromatography showed that their complete recovery was granted. The NMR analysis enabled detection and quantification of unknown impurities without the need of pure compounds as internal standards.

Integration of gold-sputtered electrofluidic paper on wire-included analytical platforms for glucose biosensing.

PubMed

Núnez-Bajo, Estefanía; Carmen Blanco-López, M; Costa-García, Agustín; Teresa Fernández-Abedul, M

2017-05-15

This work describes the fabrication and evaluation of an electroanalytical paper-based platform based on the combination of both, reusable and disposable materials in order to generate simple, versatile and low-cost microfluidic devices. With this aim, a holder containing metal wires that act as reusable reference and counter electrodes has been developed. The gold-sputtered paper electrode is disposable and easily interchangeable, meanwhile the platform that includes reference and counter electrodes can be reused. The detection zone in the paper is delimited by drawing a hydrophobic line with an inexpensive permanent marker. The effect of experimental variables such as adding solutions through the face where the gold was sputtered (upwards) or through the opposite one (downwards) as well as of other working parameters were studied by cyclic and differential pulse voltammetry with potassium ferrocyanide as a common redox probe and indicator species for enzymatic, immune and DNA biosensing. Enzymatic determination of glucose in real food samples prove the feasibility of the developed system for the construction of electrochemical biosensors. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparative study of different alcohol sensors based on Screen-Printed Carbon Electrodes.

PubMed

Costa Rama, Estefanía; Biscay, Julien; González García, María Begoña; Julio Reviejo, A; Pingarrón Carrazón, José Manuel; Costa García, Agustín

2012-05-30

Different very simple single-use alcohol enzyme sensors were developed using alcohol oxidase (AOX) from three different yeast, Hansenula sp., Pichia pastoris and Candida boidinii, and employing three different commercial mediator-based Screen-Printed Carbon Electrodes as transducers. The mediators tested, Prussian Blue, Ferrocyanide and Co-phthalocyanine were included into the ink of the working electrode. The procedure to obtain these sensors consists of the immobilization of the enzyme on the electrode surface by adsorption. For the immobilization, an AOX solution is deposited on the working electrode and left until dried (1h) at room temperature. The best results were obtained with the biosensor using Screen-Printed Co-phthalocyanine/Carbon Electrode and AOX from Hansenula sp. The reduced cobalt-phthalocyanine form is amperometrically detected at +0.4V (vs. Ag pseudo reference electrode). This sensor shows good sensitivity (1211 nA mM(-1)), high precision (2.1% RSD value for the slope value of the calibration plot) and wide linear response (0.05-1.00 mM) for ethanol determination. The sensor provides also accurate results for ethanol quantification in alcoholic drinks. Copyright © 2012 Elsevier B.V. All rights reserved.

Real-time mapping of salt glands on the leaf surface of Cynodon dactylon L. using scanning electrochemical microscopy.

PubMed

Parthasarathy, Meera; Pemaiah, Brindha; Natesan, Ravichandran; Padmavathy, Saralla R; Pachiappan, Jayaraman

2015-02-01

Salt glands are specialized organelles present in the leaf tissues of halophytes, which impart salt-tolerance capability to the plant species. These glands are usually identified only by their morphology using conventional staining procedures coupled with optical microscopy. In this work, we have employed scanning electrochemical microscopy to identify the salt glands not only by their morphology but also by their salt excretion behavior. Bermuda grass (Cynodon dactylon L.) species was chosen for the study as they are known to be salt-tolerant and contain salt glands on leaf surfaces. Scanning electrochemical microscopy performed in sodium chloride medium in the presence and absence of potassium ferrocyanide as redox mediator, reveals the identity of salt glands. More insight into the ion expulsion behavior of these glands was obtained by mapping lateral and vertical variations in ion concentrations using surface impedance measurements which indicated five times higher resistance over the salt glands compared to the surrounding tissues and bulk solution. The protocol could be used to understand the developmental processes in plants grown in different soil/water conditions in order to improve salt tolerance of food crops by genetic engineering and hence improve their agricultural productivity.

The structure of PbCl2 on the {100} surface of NaCl and its consequences for crystal growth

NASA Astrophysics Data System (ADS)

Townsend, Eleanor R.; Brugman, Sander J. T.; Blijlevens, Melian A. R.; Smets, Mireille M. H.; de Poel, Wester; van Enckevort, Willem J. P.; Meijer, Jan A. M.; Vlieg, Elias

2018-04-01

The role that additives play in the growth of sodium chloride is a topic which has been widely researched but not always fully understood at an atomic level. Lead chloride (PbCl2) is one such additive which has been reported to have growth inhibition effects on NaCl {100} and {111}; however, no definitive evidence has been reported which details the mechanism of this interaction. In this investigation, we used the technique of surface x-ray diffraction to determine the interaction between PbCl2 and NaCl {100} and the structure at the surface. We find that Pb2+ replaces a surface Na+ ion, while a Cl- ion is located on top of the Pb2+. This leads to a charge mismatch in the bulk crystal, which, as energetically unfavourable, leads to a growth blocking effect. While this is a similar mechanism as in the anticaking agent ferrocyanide, the effect of PbCl2 is much weaker, most likely due to the fact that the Pb2+ ion can more easily desorb. Moreover, PbCl2 has an even stronger effect on NaCl {111}.

Integrating Reverse-Electrodialysis Stacks with Flow Batteries for Improved Energy Recovery from Salinity Gradients and Energy Storage.

PubMed

Zhu, Xiuping; Kim, Taeyoung; Rahimi, Mohammad; Gorski, Christopher A; Logan, Bruce E

2017-02-22

Salinity gradient energy can be directly converted into electrical power by using reverse electrodialysis (RED) and other technologies, but reported power densities have been too low for practical applications. Herein, the RED stack performance was improved by using 2,6-dihydroxyanthraquinone and ferrocyanide as redox couples. These electrolytes were then used in a flow battery to produce an integrated RED stack and flow battery (RED-FB) system capable of capturing, storing, and discharging salinity gradient energy. Energy captured from the RED stack was discharged in the flow battery at a maximum power density of 3.0 kW m -2 -anode, which was similar to the flow batteries charged by electrical power and could be used for practical applications. Salinity gradient energy captured from the RED stack was recovered from the electrolytes as electricity with 30 % efficiency, and the maximum energy density of the system was 2.4 kWh m -3 -anolyte. The combined RED-FB system overcomes many limitations of previous approaches to capture, store, and use salinity gradient energy from natural or engineered sources. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Binding of Phenazinium Dye Safranin T to Polyriboadenylic Acid: Spectroscopic and Thermodynamic Study

PubMed Central

Roy, Snigdha; Das, Suman

2014-01-01

Here, we report results from experiments designed to explore the association of the phenazinium dye safranin T (ST, 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride) with single and double stranded form of polyriboadenylic acid (hereafter poly-A) using several spectroscopic techniques. We demonstrate that the dye binds to single stranded polyriboadenylic acid (hereafter ss poly-A) with high affinity while it does not interact at all with the double stranded (ds) form of the polynucleotide. Fluorescence and absorption spectral studies reveal the molecular aspects of binding of ST to single stranded form of the polynucleotide. This observation is also supported by the circular dichroism study. Thermodynamic data obtained from temperature dependence of binding constant reveals that association is driven by negative enthalpy change and opposed by negative entropy change. Ferrocyanide quenching studies have shown intercalative binding of ST to ss poly-A. Experiments on viscosity measurements confirm the binding mode of the dye to be intercalative. The effect of [Na+] ion concentration on the binding process suggests the role of electrostatic forces in the complexation. Present studies reveal the utility of the dye in probing nucleic acid structure. PMID:24498422

Binding of phenazinium dye safranin T to polyriboadenylic acid: spectroscopic and thermodynamic study.

PubMed

Pradhan, Ankur Bikash; Haque, Lucy; Roy, Snigdha; Das, Suman

2014-01-01

Here, we report results from experiments designed to explore the association of the phenazinium dye safranin T (ST, 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride) with single and double stranded form of polyriboadenylic acid (hereafter poly-A) using several spectroscopic techniques. We demonstrate that the dye binds to single stranded polyriboadenylic acid (hereafter ss poly-A) with high affinity while it does not interact at all with the double stranded (ds) form of the polynucleotide. Fluorescence and absorption spectral studies reveal the molecular aspects of binding of ST to single stranded form of the polynucleotide. This observation is also supported by the circular dichroism study. Thermodynamic data obtained from temperature dependence of binding constant reveals that association is driven by negative enthalpy change and opposed by negative entropy change. Ferrocyanide quenching studies have shown intercalative binding of ST to ss poly-A. Experiments on viscosity measurements confirm the binding mode of the dye to be intercalative. The effect of [Na⁺] ion concentration on the binding process suggests the role of electrostatic forces in the complexation. Present studies reveal the utility of the dye in probing nucleic acid structure.

The effects of ultraviolet-B radiation on the toxicity of fire-fighting chemicals

USGS Publications Warehouse

Calfee, R.D.; Little, E.E.

2003-01-01

The interactive effects of ultraviolet (UV) and fire-retardant chemicals were evaluated by exposing rainbow trout (Oncorhyncus mykiss) juveniles and tadpoles of southern leopard frogs (Rana sphenocephala) to six fire-retardant formulations with and without sodium ferrocyanide (yellow prussiate of soda [YPS]) and to YPS alone under three simulated UV light treatments. Yellow prussiate of soda is used as a corrosion inhibitor in some of the fire-retardant chemical formulations. The underwater UV intensities measured were about 2 to 10% of surface irradiance measured in various aquatic habitats and were within tolerance limits for the species tested. Mortality of trout and tadpoles exposed to Fire-Trol?? GTS-R, Fire-Trol 300-F, Fire-Trol LCA-R, and Fire-Trol LCA-F was significantly increased in the presence of UV radiation when YPS was present in the formulation. The boreal toad (Bufo boreas), listed as endangered by the state of Colorado (USA), and southern leopard frog were similar in their sensitivity to these chemicals. Photoenhancement of fire-retardant chemicals can occur in a range of aquatic habitats and may be of concern even when optical clarity of water is low; however, other habitat characteristics can also reduce fire retardant toxicity.

Ultrastructural and cytochemical evidence for single impulse initiation zones in vestibular macular nerve fibers of rat

NASA Technical Reports Server (NTRS)

Ross, Muriel D.; Chee, Oliver; Black, Samuel; Cutler, Lynn

1991-01-01

Cupric ion-ferricyanide labeling methods and related ferrocyanide-stained tissues were used to locate the characterize, at the ultrastructural level, presumptive impulse initiation zones in the three types of vestibular macular nerve fibers. Large-diameter, M-type vestibular nerve fibers terminate in a calyx at the heminode, and labeling is coextensive with the base of the calyx. Intermediate, M/U-type nerve fibers have short, unmyelinated preterminal segments that sometimes bifurcate intamacularly, and small-diameter, U-type nerve fibers have long, unmyelinated preterminal axons and up to three branches. Preterminals of these nerve fibers display ultrastructural heterogeneity that is correlated with labeling patterns for sodium channels and/or associated polyanionic sites. They have a nodelike ultrastructure and label heavily from near the heminode to the base of the macula. Their intramacular branches, less organized ultrastructurally, label only slightly. Results indicate that vestibular nerve fibers have one impulse initiation zone, located near the heminode, that varies in length according to nerve fiber type. Structural heterogeneity may favor impulse conduction in the central direction, and length of the impulse initiation zone could influence nerve discharge patterns.

Impaired succinic dehydrogenase activity of rat Purkinje cell mitochondria during aging.

PubMed

Fattoretti, P; Bertoni-Freddari, C; Caselli, U; Paoloni, R; Meier-Ruge, W

1998-03-16

The perikaryal Purkinje cell mitochondria positive to the copper ferrocyanide histochemical reaction for succinic dehydrogenase (SDH) have been investigated by means of semiautomatic morphometric methods in rats of 3, 12 and 24 months of age. The number of organelles/microm3 of Purkinje cell cytoplasm (Numeric density: Nv), the average mitochondrial volume (V) and the mitochondrial volume fraction (Volume density: Vv) were the ultrastructural parameters taken into account. Nv was significantly higher at 12 than at 3 and 24 months of age. V was significantly decreased at 12 and 24 months of age, but no difference was envisaged between adult and old rats. Vv was significantly decreased in old animals vs. the other age groups. In young and old rats, the percentage of organelles larger than 0.32 microm3 was 13.5 and 11%, respectively, while these enlarged mitochondria accounted for less than 1% in the adult group. Since SDH activity is of critical importance when energy demand is high, the marked decrease of Vv supports an impaired capacity of the old Purkinje cells to match actual energy supply at sustained transmission of the nervous impulse. However, the high percentage of enlarged organelles found in old rats may witness a morphofunctional compensatory response.

FINE STRUCTURAL LOCALIZATION OF ACYLTRANSFERASES

PubMed Central

Higgins, Joan A.; Barrnett, Russell J.

1971-01-01

A study of the fine structural localization of the acyltransferases of the monoglyceride and α-glycerophosphate pathways for triglyceride synthesis in the intestinal absorptive cell is reported. Glutaraldehyde-fixed tissue was found to synthesize diglyceride and triglyceride from monopalmitin and palmityl CoA, and parallel morphological studies showed the appearance of lipid droplets in the smooth endoplasmic reticulum of the absorptive cell. Glutaraldehyde-fixed tissue also synthesized triglyceride from α-glycerophosphate, although this enzyme system was more susceptible to fixation than the monoglyceride pathway acyltransferases. Cytochemical methods for the localization of free CoA were based (a) on the formation of the insoluble lanthanium mercaptide of CoA and (b) on the reduction of ferricyanide by CoA to yield ferrocyanide which forms an insoluble precipitate with manganous ions. By these methods the monoglyceride pathway acyltransferases were found to be located mainly on the inner surface of the smooth endoplasmic reticulum. The α-glycerophosphate pathway acyltransferases were localized mainly on the rough endoplasmic reticulum. Activity limited to the outer cisternae of the Golgi membranes occurred with both pathways. The possible organization of triglyceride absorption and chylomicron synthesis is discussed in view of these results. PMID:5563442

Vapor space characterization of Waste Tank 241-TY-104 (in situ): Results from samples collected on 8/5/94

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

Ligotke, M.W.; Pool, K.H.; Lucke, R.B.

1995-10-01

This report describes inorganic and organic analyses results from in situ samples obtained from the headspace of the Hanford waste storage Tank 241-TY-104 (referred to as Tank TY-104). The results described here were obtained to support safety and toxicological evaluations. A summary of the results for inorganic and organic analytes is listed in Table 1. Detailed descriptions of the results appear in the text. Quantitative results were obtained for the inorganic compounds ammonia (NH{sub 3}), nitrogen dioxide (NO{sub 2}), nitric oxide (NO), and water (H{sub 2}O). Sampling for hydrogen cyanide (HCN) and sulfur oxides (SO{sub x}) was not performed. Inmore » addition, the authors looked for the 39 TO-14 compounds plus an additional 14 analytes. Of these, eight were observed above the 5-ppbv reporting cutoff. Twenty-four organic tentatively identified compounds (TICs) were observed above the reporting cutoff of (ca.) 10 ppbv and are reported with concentrations that are semiquantitative estimates based on internal standard response factors. The 10 organic analytes with the highest estimated concentrations are listed in Table 1 and account for approximately 86% of the total organic components in Tank TY-104. Tank TY-104 is on the Ferrocyanide Watch List.« less

Fabrication and characterization of electrochemically prepared bioanode (polyaniline/ferritin/glucose oxidase) for biofuel cell application

NASA Astrophysics Data System (ADS)

ul Haque, Sufia; Inamuddin; Nasar, Abu; Asiri, Abdullah M.

2018-01-01

Porous matrix of polyaniline (PANI) has been electrodeposited along with the entrapment of biocompatible redox mediator ferritin (Frt) and glucose oxidase (GOx) on the surface of glassy carbon (GC) electrode. The characterizations have been carried out by X-ray Diffraction (XRD) and Transmission electron microscopy (TEM). The enhanced electrochemical signal transfer rate from enzyme to the electrode surface was due to the intimate contact of the enzyme with the electrochemically polymerized conducting PANI matrix. The PANI/Frt/GOx modified GC bioanode was used to investigate the electrocatalytic activity as a function of the concentration of glucose in the range of 10-60 mM. It was confirmed by the electrochemical impedance spectroscopy (EIS), the thick deposition of PANI layer becomes more compact due to which the charge transfer resistance of PANI matrix becomes higher. All the electrochemical measurements of the electrode were carried out by using cyclic voltammetry (CV) and linear sweep voltammetry (LSV). CV curves were recorded at different scan rates (20-100 mV/s) at 50 mM of glucose in 0.3 M potassium ferrocyanide. A normalized saturation current density of 22.3 ± 2 mA/cm2 was observed for the oxidation of 50 mM glucose at a scan rate of 100 mV/s.

Monitoring intra- and extracellular redox capacity of intact barley aleurone layers responding to phytohormones.

PubMed

Mark, Christina; Zór, Kinga; Heiskanen, Arto; Dufva, Martin; Emnéus, Jenny; Finnie, Christine

2016-12-15

Redox regulation is important for numerous processes in plant cells including abiotic stress, pathogen defence, tissue development, seed germination and programmed cell death. However, there are few methods allowing redox homeostasis to be addressed in whole plant cells, providing insight into the intact in vivo environment. An electrochemical redox assay that applies the menadione-ferricyanide double mediator is used to assess changes in the intracellular and extracellular redox environment in living aleurone layers of barley (Hordeum vulgare cv. Himalaya) grains, which respond to the phytohormones gibberellic acid and abscisic acid. Gibberellic acid is shown to elicit a mobilisation of electrons as detected by an increase in the reducing capacity of the aleurone layers. By taking advantage of the membrane-permeable menadione/menadiol redox pair to probe the membrane-impermeable ferricyanide/ferrocyanide redox pair, the mobilisation of electrons was dissected into an intracellular and an extracellular, plasma membrane-associated component. The intracellular and extracellular increases in reducing capacity were both suppressed when the aleurone layers were incubated with abscisic acid. By probing redox levels in intact plant tissue, the method provides a complementary approach to assays of reactive oxygen species and redox-related enzyme activities in tissue extracts. Copyright © 2016 Elsevier Inc. All rights reserved.

Restoration of water environment contaminated by radioactive cesium released from Fukushima Daiichi NPP

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

Takeshita, K.; Takahashi, H.; Jinbo, Y.

2013-07-01

In the Fukushima Daiichi NPP Accident, large amounts of volatile radioactive nuclides, such as {sup 131}I, {sup 134}Cs and {sup 137}Cs, were released to the atmosphere and huge areas surrounding the nuclear site were contaminated by the radioactive fallout. In this study, a combined process with a hydrothermal process and a coagulation settling process was proposed for the separation of radioactive Cs from contaminated soil and sewage sludge. The coagulation settling operation uses Prussian Blue (Ferric ferrocyanide) and an inorganic coagulant. The recovery of Cs from sewage sludge sampled at Fukushima city (100.000 Bq/kg) and soil at a nearby villagemore » (55.000 Bq/kg), was tested. About 96% of Cs in the sewage sludge was removed successfully by combining simple hydrothermal decomposition and coagulation settling. However, Cs in the soil was not removed sufficiently by the combined process (Cs removal is only 56%). The hydrothermal decomposition with blasting was carried out. The Cs removal from the soil was increased to 85%. When these operations were repeated twice, the Cs recovery was over 90%. The combined process with hydrothermal blasting and coagulation settling is applicable to the removal of Cs from highly contaminated soil.« less

Multienzymatic amperometric biosensor based on gold and nanocomposite planar electrodes for glycerol determination in wine.

PubMed

Monošík, Rastislav; Ukropcová, Dana; Streďanský, Miroslav; Šturdík, Ernest

2012-02-01

Amperometric biosensors based on gold planar or nanocomposite electrode containing multiwalled carbon nanotubes for determination of glycerol were developed. The biosensors were constructed by immobilization of a novel multienzyme cascade consisting of glycerol kinase/creatine kinase/creatinase/sarcosine oxidase/peroxidase between a chitosan "sandwich." A measuring buffer contained adenosine 5'-triphosphate (ATP), creatine phosphate, and an artificial electrochemical mediator ferrocyanide. The currents proportional to glycerol concentration were measured at working potential of -50 mV against Ag/AgCl reference electrode. The biosensors showed linearity over the ranges of 5-640 μM and 5-566 μM with detection limits of 1.96 and 2.24 μM and sensitivities of 0.80 and 0.81 nA μM(-1), respectively. Both types of biosensors had a response time of 70s. The biosensors demonstrated satisfactory operational stability (no loss of sensitivity after 90 consecutive measurements) and excellent storage stability (90% of the initial sensitivity after 15 months of storage at room temperature). The results obtained from measurements of wines correlated well with those obtained with an enzymatic-spectrophotometric assay. The presented multienzyme cascade can be used also for determination of triglycerides or various kinase substrates when glycerol kinase is replaced by other kinases. Copyright © 2011 Elsevier Inc. All rights reserved.

Pin-based electrochemical glucose sensor with multiplexing possibilities.

PubMed

Rama, Estefanía C; Costa-García, Agustín; Fernández-Abedul, M Teresa

2017-02-15

This work describes the use of mass-produced stainless-steel pins as low-cost electrodes to develop simple and portable amperometric glucose biosensors. A potentiostatic three-electrode configuration device is designed using two bare pins as reference and counter electrodes, and a carbon-ink coated pin as working electrode. Conventional transparency film without any pretreatment is used to punch the pins and contain the measurement solution. The interface to the potentiostat is very simple since it is based on a commercial female connection. This electrochemical system is applied to glucose determination using a bienzymatic sensor phase (glucose oxidase/horseradish peroxidase) with ferrocyanide as electron-transfer mediator, achieving a linear range from 0.05 to 1mM. It shows analytical characteristics comparable to glucose sensors previously reported using conventional electrodes, and its application for real food samples provides good results. The easy modification of the position of the pins allows designing different configurations with possibility of performing simultaneous measurements. This is demonstrated through a specific design that includes four pin working-electrodes. Different concentrations of antibody labeled with alkaline phosphatase are immobilized on the pin-heads and after enzymatic conversion of 3-indoxylphosphate and silver nitrate, metallic silver is determined by anodic stripping voltammetry. Copyright © 2016 Elsevier B.V. All rights reserved.

Exploring the electrochemical performance of graphitic paste electrodes: graphene vs. graphite.

PubMed

Figueiredo-Filho, Luiz C S; Brownson, Dale A C; Gómez-Mingot, Maria; Iniesta, Jesús; Fatibello-Filho, Orlando; Banks, Craig E

2013-11-07

We report the fabrication, characterisation (SEM, TEM, XPS and Raman spectroscopy) and electrochemical implementation of a graphene paste electrode. The paste electrodes utilised are constructed by simply mixing graphene with mineral oil (which acts as a binder) prior to loading the resultant paste into a piston-driven polymeric-tubing electrode-shell, where this electrode configuration allows for rapid renewal of the electrode surface. The fabricated paste electrode is electrochemically characterised using both inner-sphere and outer-sphere redox probes, namely potassium ferrocyanide(ii), hexaammine-ruthenium(iii) chloride and hexachloroiridate(iii), in addition to the biologically relevant and electroactive analytes, l-ascorbic acid (AA) and uric acid (UA). Comparisons are made with a graphite paste alternative and the benefits of graphene implementation as a paste electrode within electrochemistry are explored, as well as the characterisation of their electroanalytical performances. We reveal no observable differences in the electrochemical performance and thus suggest that there are no advantages of using graphene over graphite in the fabrication of paste electrodes. Such work is highly important and informative for those working in the field of electroanalysis where electrochemistry can provide portable, rapid, reliable and accurate sensing protocols (bringing the laboratory into the field), with particular relevance to those searching for new electrode materials.

The Electrochemical Behavior of Carbon Fiber Microelectrodes Modified with Carbon Nanotubes Using a Two-Step Electroless Plating/Chemical Vapor Deposition Process

PubMed Central

Lu, Longsheng; Liang, Linsheng; Teh, Kwok Siong; Xie, Yingxi; Wan, Zhenping; Tang, Yong

2017-01-01

Carbon fiber microelectrode (CFME) has been extensively applied in the biosensor and chemical sensor domains. In order to improve the electrochemical activity and sensitivity of the CFME, a new CFME modified with carbon nanotubes (CNTs), denoted as CNTs/CFME, was fabricated and investigated. First, carbon fiber (CF) monofilaments grafted with CNTs (simplified as CNTs/CFs) were fabricated in two key steps: (i) nickel electroless plating, followed by (ii) chemical vapor deposition (CVD). Second, a single CNTs/CF monofilament was selected and encapsulated into a CNTs/CFME with a simple packaging method. The morphologies of as-prepared CNTs/CFs were characterized by scanning electron microscopy. The electrochemical properties of CNTs/CFMEs were measured in potassium ferrocyanide solution (K4Fe(CN)6), by using a cyclic voltammetry (CV) and a chronoamperometry method. Compared with a bare CFME, a CNTs/CFME showed better CV curves with a higher distinguishable redox peak and response current; the higher the CNT content was, the better the CV curves were. Because the as-grown CNTs significantly enhanced the effective electrode area of CNTs/CFME, the contact area between the electrode and reactant was enlarged, further increasing the electrocatalytic active site density. Furthermore, the modified microelectrode displayed almost the same electrochemical behavior after 104 days, exhibiting remarkable stability and outstanding reproducibility. PMID:28358344

Environmental Assessment: Waste Tank Safety Program, Hanford Site, Richland, Washington

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

Not Available

1994-02-01

The US Department of Energy (DOE) needs to take action in the near-term, to accelerate resolution of waste tank safety issues at the Hanford Site near the City of Richland, Washington, and reduce the risks associated with operations and management of the waste tanks. The DOE has conducted nuclear waste management operations at the Hanford Site for nearly 50 years. Operations have included storage of high-level nuclear waste in 177 underground storage tanks (UST), both in single-shell tank (SST) and double-shell tank configurations. Many of the tanks, and the equipment needed to operate them, are deteriorated. Sixty-seven SSTs are presumedmore » to have leaked a total approximately 3,800,000 liters (1 million gallons) of radioactive waste to the soil. Safety issues associated with the waste have been identified, and include (1) flammable gas generation and episodic release; (2) ferrocyanide-containing wastes; (3) a floating organic solvent layer in Tank 241-C-103; (4) nuclear criticality; (5) toxic vapors; (6) infrastructure upgrades; and (7) interim stabilization of SSTs. Initial actions have been taken in all of these areas; however, much work remains before a full understanding of the tank waste behavior is achieved. The DOE needs to accelerate the resolution of tank safety concerns to reduce the risk of an unanticipated radioactive or chemical release to the environment, while continuing to manage the wastes safely.« less

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

Walser, M.; Robinson, B.H.B.

The ratio of excreted (Sr/sub u/) to filtered (Sr/sub o/) radiostrontium (Sr/sup 85/) was compared with the ratio of excreted (Ca/sub u/) to filtered (Ca/ sub o/) calcium in human subjects and dogs undergoing a variety of diuretic procedures. The relation Sr/sub u//Sr/sub o/ = (Ca/sub u/,/Ca/sub o//sup 0.7/ serves to predict Sr/sub u//Sr/sub o/ from Ca/su b u//Ca/sub o/with a standard error of estimate of 15% over a wide range of variation (30- to 200-fold) in the 2 quantities. The equation can be derived from the assumptions that the 2 ions are reabsorbed at rates proportional to the localmore » concentrations in the tubular fluid, and that the rate constant for Sr reabsorption is always 0.7 times that for Ca reabsorption. This relation was not affected by adrenocortical activity (in man), parathyroid activity, hypercalcemia, acid-base balance, Mg clearance, or diuretics (chlorothiazide or hydrochlorothiazide). Sulfate or ferrocyanide infusion was also without effect, presumably because the affinity of each of the 2 anions for Ca is similar to its affinity for Sr. Citrate, which binds Ca more strongly, diminishes renal discrimination between Ca and Sr. Although this relation has high predictive value (r* = 0.98), it does not establish that the reabsorption of Ca and Sr are first-order processes nor that the 2 ions share a common mechanism. (H.H.D.)« less

Reagentless and calibrationless silicate measurement in oceanic waters.

PubMed

Giraud, William; Lesven, Ludovic; Jońca, Justyna; Barus, Carole; Gourdal, Margaux; Thouron, Danièle; Garçon, Véronique; Comtat, Maurice

2012-08-15

Determination of silicate concentration in seawater without addition of liquid reagents was the key prerequisite for developing an autonomous in situ electrochemical silicate sensor (Lacombe et al., 2007) [11]. The present challenge is to address the issue of calibrationless determination. To achieve such an objective, we chose chronoamperometry performed successively on planar microelectrode (ME) and ultramicroelectrode (UME) among the various possibilities. This analytical method allows estimating simultaneously the diffusion coefficient and the concentration of the studied species. Results obtained with ferrocyanide are in excellent agreement with values of the imposed concentration and diffusion coefficient found in the literature. For the silicate reagentless method, successive chronoamperometric measurements have been performed using a pair of gold disk electrodes for both UME and ME. Our calibrationless method was tested with different concentrations of silicate in artificial seawater from 55 to 140×10(-6) mol L(-1). The average value obtained for the diffusion coefficient of the silicomolybdic complex is 2.2±0.4×10(-6) cm(2) s(-1), consistent with diffusion coefficient values of molecules in liquid media. Good results were observed when comparing known concentration of silicate with experimentally derived ones. Further work is underway to explore silicate determination within the lower range of oceanic silicate concentration, down to 0.1×10(-6) mol L(-1). Copyright © 2012 Elsevier B.V. All rights reserved.

Gastight Hydrodynamic Electrochemistry: Design for a Hermetically Sealed Rotating Disk Electrode Cell.

PubMed

Jung, Suho; Kortlever, Ruud; Jones, Ryan J R; Lichterman, Michael F; Agapie, Theodor; McCrory, Charles C L; Peters, Jonas C

2017-01-03

Rotating disk electrodes (RDEs) are widely used in electrochemical characterization to analyze the mechanisms of various electrocatalytic reactions. RDE experiments often make use of or require collection and quantification of gaseous products. The combination of rotating parts and gaseous analytes makes the design of RDE cells that allow for headspace analysis challenging due to gas leaks at the interface of the cell body and the rotator. In this manuscript we describe a new, hermetically sealed electrochemical cell that allows for electrode rotation while simultaneously providing a gastight environment. Electrode rotation in this new cell design is controlled by magnetically coupling the working electrode to a rotating magnetic driver. Calibration of the RDE using a tachometer shows that the rotation speed of the electrode is the same as that of the magnetic driver. To validate the performance of this cell for hydrodynamic measurements, limiting currents from the reduction of a potassium ferrocyanide (K 4 [Fe(CN) 6 ]·3H 2 O) were measured and shown to compare favorably with calculated values from the Levich equation and with data obtained using more typical, nongastight RDE cells. Faradaic efficiencies of ∼95% were measured in the gas phase for oxygen evolution in alkaline media at an Inconel 625 alloy electrocatalyst during rotation at 1600 rpm. These data verify that a gastight environment is maintained even during rotation.

Road de-icing salt as a potential constraint on urban growth in the Greater Toronto Area, Canada

NASA Astrophysics Data System (ADS)

Howard, Ken W. F.; Maier, Herb

2007-04-01

North America's fifth most populated municipality — the Greater Toronto Area (GTA) — is undergoing rapid urban development with serious questions being raised regarding the long-term impacts of urban growth on the quality and quantity of ground and surface water. Degradation of groundwater quality by NaCl de-icing salt is the primary concern since there are no cost effective alternatives to NaCl de-icing salt and there is little evidence that salt loadings to the subsurface can be significantly reduced. In 2001, the issue acquired a new sense of urgency when de-icing chemicals containing inorganic chloride salts (with or without ferrocyanide de-caking agents) were designated as toxic under the Canadian Environmental Protection Act. To heighten concerns, future growth in the GTA will inevitably take place in areas where groundwater is regularly used for potable supply. Studies using groundwater flow and transport models show that significant deterioration of groundwater quality can be expected in shallow aquifers as a result of urban development with chloride concentrations approaching the drinking water quality standard of 250 mg/l. Results demonstrate that urban planning needs a fresh approach that explicitly includes groundwater protection and aquifer management in the decision-making process, clearly defines acceptable environmental performance standards and makes greater use of groundwater models to evaluate alternative urban designs.

High-throughput screening for cellobiose dehydrogenases by Prussian Blue in situ formation.

PubMed

Vasilchenko, Liliya G; Ludwig, Roland; Yershevich, Olga P; Haltrich, Dietmar; Rabinovich, Mikhail L

2012-07-01

Extracellular fungal flavocytochrome cellobiose dehydrogenase (CDH) is a promising enzyme for both bioelectronics and lignocellulose bioconversion. A selective high-throughput screening assay for CDH in the presence of various fungal oxidoreductases was developed. It is based on Prussian Blue (PB) in situ formation in the presence of cellobiose (<0.25 mM), ferric acetate, and ferricyanide. CDH induces PB formation via both reduction of ferricyanide to ferrocyanide reacting with an excess of Fe³⁺ (pathway 1) and reduction of ferric ions to Fe²⁺ reacting with the excess of ferricyanide (pathway 2). Basidiomycetous and ascomycetous CDH formed PB optimally at pH 3.5 and 4.5, respectively. In contrast to the holoenzyme CDH, its FAD-containing dehydrogenase domain lacking the cytochrome domain formed PB only via pathway 1 and was less active than the parent enzyme. The assay can be applied on active growing cultures on agar plates or on fungal culture supernatants in 96-well plates under aerobic conditions. Neither other carbohydrate oxidoreductases (pyranose dehydrogenase, FAD-dependent glucose dehydrogenase, glucose oxidase) nor laccase interfered with CDH activity in this assay. Applicability of the developed assay for the selection of new ascomycetous CDH producers as well as possibility of the controlled synthesis of new PB nanocomposites by CDH are discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-pot preparation of conducting composite containing abundant amino groups on electrode surface for electrochemical detection of von willebrand factor

NASA Astrophysics Data System (ADS)

Wang, Wen; Ma, Chao; Li, Yi; Liu, Baihui; Tan, Liang

2018-03-01

A one-pot protocol based on cyclic voltammetric scan was employed to prepare new conducting composite that was abundant in amino groups. The scanning electron microscope, atomic force microscope, X-ray photoelectron spectroscopy and infrared spectrum characterization demonstrate that poly(azure A), gold nanoparticles, chitosan and cysteine were immobilized simultaneously on glassy carbon electrode surface. Von Willebrand factor (vWF) antibody (Ab) was subsequently assembled by using glutaraldehyde to construct the Ab/composite-modified electrode. The capture of vWF could inhibit the charge transfer between the ferri-/ferrocyanide probe and the electrode and exert the negative effect on the electrochemical response of the dye polymer in the conducting composite due to the strong steric hindrance effect. The DPV peak current change before and after the immunoreaction was found to be proportional to the logarithm of the vWF concentration from 0.001 to 100 μg mL-1 with a detection limit of 0.4 ng mL-1. The proposed label-free electrochemical method was employed in the investigation on the release of vWF by oxidation-injured vascular endothelial cells. The experimental results exhibit that the vWF content in growth medium was increased when the oxidation injury of the cells was intensified in the presence of H2O2.

Application of sorption technique for decontamination of liquid radwaste and natural water from cesium and strontium radionuclides

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

Milyutin, V.V.; Gelis, V.M.; Penzin, R.A.

1995-12-31

In this paper the results obtained in field tests of decontaminating radioactive natural and industrial solutions of different chemical and radionuclide composition from cesium and strontium radionuclides are reported. Decontamination of industrial reservoir water at the Production Association Mayak (Chelyabinsk Region, Russia) was performed using CMP synthetic zeolite. Efficient decontamination of the feed water is achieved after preliminary precipitation of hardness salts in the form of carbonates. Decontamination of water from the pool for spent fuel element storage from {sup 137}Cs was conducted using NGA ferricyanide sorbent. Decontamination factors with respect to {sup 137}Cs of 400 have been reached, themore » installation throughput being 100,000 by (bed volumes). Decontamination of liquid radwaste at Murmansk Shipping Co was conducted with CFB, CMP synthetic zeolites and NGA ferricyanide sorbent as well. Decontamination of D and D solutions and wastes of the special laundry resulted in decontamination factors within the range of 20--400, 10--100, and 10--30 with respect to {sup 137}Cs, {sup 90}Sr, and total {beta}-activity, respectively. Installation throughput of 3,000--5,000 bv for zeolites and 8,000--10,000 bv for ferrocyanide sorbents has been reached. Results obtained prove the high efficiency of sorption technique for decontaminating solutions from cesium and strontium radionuclides.« less

K4[Fe(CN)6] immobilized anion sensitive protonated amine functionalized polysilsesquioxane films for ultra-low electrochemical detection of dsDNA.

PubMed

Silambarasan, Krishnamoorthy; Narendra Kumar, Alam Venugopal; Joseph, James

2016-03-14

Charge transport in polymeric films bound by redox reagents is a topic of current interest. The dynamics of electroinactive ions across the interface is studied by immobilizing ferrocyanide anion in a polysilsesquioxanes (PSQs) modified electrode. Redox reagents can stay in the polymeric film by either physical forces or electrostatic binding. The present work describes the immobilization of ferro/ferricyanide redox couples in PSQ films possessing protonated amine functional groups by electrostatic interactions. Charge transport in [Fe(CN)6](4-)-PSQs film was found to be anion dependent, and its formal potential value varied with the relative hydrophilic or hydrophobic nature of the anion used in the supporting electrolyte, unlike the observed dependence on solution cation for electrodes modified with metal hexacyanoferrates (Prussian Blue analogues). The [Fe(CN)6](4-) bound PSQs films were extensively characterized by varying different supporting electrolytes anions using cyclic voltammetry. The redox peak currents were linearly proportional to the square root of the scan rate, implying that the transport of charge carriers is accompanied with redox ion diffusion and electron hopping in a confined space. dsDNA molecules were found to interact with this polymer matrix through anionic phosphate groups. Both voltammetry and A.C. impedance spectroscopy studies revealed that these interactions could be exploited for the determination of ultra-low level (0.5 attomolar) of dsDNA present in aqueous solution.

Road de-icing salt as a potential constraint on urban growth in the Greater Toronto Area, Canada.

PubMed

Howard, Ken W F; Maier, Herb

2007-04-01

North America's fifth most populated municipality--the Greater Toronto Area (GTA)--is undergoing rapid urban development with serious questions being raised regarding the long-term impacts of urban growth on the quality and quantity of ground and surface water. Degradation of groundwater quality by NaCl de-icing salt is the primary concern since there are no cost effective alternatives to NaCl de-icing salt and there is little evidence that salt loadings to the subsurface can be significantly reduced. In 2001, the issue acquired a new sense of urgency when de-icing chemicals containing inorganic chloride salts (with or without ferrocyanide de-caking agents) were designated as toxic under the Canadian Environmental Protection Act. To heighten concerns, future growth in the GTA will inevitably take place in areas where groundwater is regularly used for potable supply. Studies using groundwater flow and transport models show that significant deterioration of groundwater quality can be expected in shallow aquifers as a result of urban development with chloride concentrations approaching the drinking water quality standard of 250 mg/l. Results demonstrate that urban planning needs a fresh approach that explicitly includes groundwater protection and aquifer management in the decision-making process, clearly defines acceptable environmental performance standards and makes greater use of groundwater models to evaluate alternative urban designs.

A facile photoelectrochemical sensor for high sensitive ROS and AA detection based on graphitic carbon nitride nanosheets.

PubMed

Motaghed Mazhabi, Robabeh; Ge, Liqin; Jiang, Hui; Wang, Xuemei

2018-06-01

Photoactive material is one of the main challenges for fabrication of sensitive and selective photoelectrochemical (PEC) sensor. Herein, a facile PEC sensor is constructed using graphitic carbon nitride nanosheets (g-C 3 N 4 NSs) coated on the surface of ITO electrode, where electron donor properties of potassium ferrocyanide and ascorbic acid is utilized for the tracing of hydrogen peroxide (H 2 O 2 ), hypochlorite (ClO - ), and ascorbic acid (AA). Our designed PEC sensor exhibits a good linear range to H 2 O 2 concentrations from 12.5 to 875 µM in pH = 7.4 and 2.5-400 µM in pH = 10, while that for AA is in the range from 0.25 to 100 µM in pH = 7.4, and with the same pH for ClO - concentrations in the range from 0.5 to 19 × 10 -3 % (V/V) in a bleach sample. Owing to the good responses towards the traces of H 2 O 2 , AA, and ClO - , our designed system may be used as H 2 O 2, ClO - , and AA sensor for outdoor applications with high specificity, long-time stability and good reproducibility. Copyright © 2018 Elsevier B.V. All rights reserved.

Biophysical Characterization of the Strong Stabilization of the RNA Triplex poly(U)•poly(A)*poly(U) by 9-O-(ω-amino) Alkyl Ether Berberine Analogs

PubMed Central

Hossain, Maidul; Haq, Lucy; Suresh Kumar, Gopinatha

2012-01-01

Background Binding of two 9-O-(ω-amino) alkyl ether berberine analogs BC1 and BC2 to the RNA triplex poly(U)•poly(A)*poly(U) was studied by various biophysical techniques. Methodology/Principal Findings Berberine analogs bind to the RNA triplex non-cooperatively. The affinity of binding was remarkably high by about 5 and 15 times, respectively, for BC1 and BC2 compared to berberine. The site size for the binding was around 4.3 for all. Based on ferrocyanide quenching, fluorescence polarization, quantum yield values and viscosity results a strong intercalative binding of BC1 and BC2 to the RNA triplex has been demonstrated. BC1 and BC2 stabilized the Hoogsteen base paired third strand by about 18.1 and 20.5°C compared to a 17.5°C stabilization by berberine. The binding was entropy driven compared to the enthalpy driven binding of berbeine, most likely due to additional contacts within the grooves of the triplex and disruption of the water structure by the alkyl side chain. Conclusions/Significance Remarkably higher binding affinity and stabilization effect of the RNA triplex by the amino alkyl berberine analogs was achieved compared to berberine. The length of the alkyl side chain influence in the triplex stabilization phenomena. PMID:22666416

Influence of Arbuscular Mycorrhizal Fungus (AMF) on degradation of iron-cyanide complexes

NASA Astrophysics Data System (ADS)

Sut, Magdalena; Boldt-Burisch, Katja; Raab, Thomas

2015-04-01

Soil contamination in the vicinities of former Manufactured Gas Plant (MGP) sites is a worldwide known environmental issue. The pollutants, in form of iron-cyanide complexes, originating from the gas purification process, create a risk for human health due to potential release of toxic free cyanide, CN(aq) and HCN(g), (aq).The management and remediation of cyanide contaminated soil can be very challenging due to the complex chemistry and toxicity of CN compounds. The employment of phytoremediation to remove or stabilize contaminants at a former MGP site is an inexpensive process, but can be limited through shallow rotting, decreased biomass, poor growing and the risk of secondary accumulation. However, this adaptation may be enhanced via arbuscular mycorrhizal fungi (AMF) activity, which may cooperate on the degradation, transformation or uptake of the contaminants. We would like to present our preliminary results from the ongoing project concerning toxic substrate-AMF-plant relation, based on studying the site of a former MGP site. In situ experiments contributed to identifying those fungi that are likely to persist in extremely acidic and toxic conditions. Subsequently, commercially available Rhizophagus irregularis was grown in sterilized, un-spiked soil with the roots of the host plant Calamagrostis epigejos. Extracted roots and AMF hyphae were used in the batch experiment, were the potential of this association on degradation of iron-cyanide complexes, in form of potassium ferrocyanide solution, was assessed.

The use of optical fiber bundles combined with electrochemistry for chemical imaging.

PubMed

Szunerits, Sabine; Walt, David R

2003-02-17

The present Review describes the progress made in using imaging optical fiber bundles for fluorescence and electrochemical-initiated chemiluminescence imaging. A novel optoelectrochemical micro-ring array has been fabricated and demonstrated for concurrent electrochemical and optical measurements. The device comprises optical fibers coated with gold via electroless gold deposition and assembled in a random array format. The design yielded an array of approximately 200 micro-ring electrodes, where interdiffusional problems were minimized. The inner diameter of the ring electrode is fixed by the diameter of the individual optical fibers (25 microns), while the outer radius is determined by the thickness of the deposited gold. While all the fibers are optically addressable, they are not all electrochemically addressable. The resolution of this device is in the tens of micrometers range, determined by the diameter of the optical fiber (25 microns) and by the spacing between each electrically connected fiber. For the purpose of having well-behaved microelectrode characteristics, this spacing was designed to be larger than 60 microns. The array was characterized using ferrocyanide in aqueous solution as a model electroactive species to demonstrate that this microelectrode array format exhibits steady-state currents at short response times. This device has potential application to be used as an optoelectronic sensor, especially for the electrolytic generation and transmission of electrochemiluminescence, and was used to demonstrate that electrochemically generated luminescent products can be detected with the fiber assembly.

Hemoglobin and Myoglobin as Reducing Agents in Biological Systems. Redox Reactions of Globins with Copper and Iron Salts and Complexes.

PubMed

Postnikova, G B; Shekhovtsova, E A

2016-12-01

In addition to reversible O2 binding, respiratory proteins of the globin family, hemoglobin (Hb) and myoglobin (Mb), participate in redox reactions with various metal complexes, including biologically significant ones, such as those of copper and iron. HbO 2 and MbO 2 are present in cells in large amounts and, as redox agents, can contribute to maintaining cell redox state and resisting oxidative stress. Divalent copper complexes with high redox potentials (E 0 , 200-600 mV) and high stability constants, such as [Cu(phen) 2 ] 2+ , [Cu(dmphen) 2 ] 2+ , and CuDTA oxidize ferrous heme proteins by the simple outer-sphere electron transfer mechanism through overlapping π-orbitals of the heme and the copper complex. Weaker oxidants, such as Cu2+, CuEDTA, CuNTA, CuCit, CuATP, and CuHis (E 0 ≤ 100-150 mV) react with HbO 2 and MbO 2 through preliminary binding to the protein with substitution of the metal ligands with protein groups and subsequent intramolecular electron transfer in the complex (the site-specific outer-sphere electron transfer mechanism). Oxidation of HbO 2 and MbO 2 by potassium ferricyanide and Fe(3) complexes with NTA, EDTA, CDTA, ATP, 2,3-DPG, citrate, and pyrophosphate PP i proceeds mainly through the simple outer-sphere electron transfer mechanism via the exposed heme edge. According to Marcus theory, the rate of this reaction correlates with the difference in redox potentials of the reagents and their self-exchange rates. For charged reagents, the reaction may be preceded by their nonspecific binding to the protein due to electrostatic interactions. The reactions of LbO 2 with carboxylate Fe complexes, unlike its reactions with ferricyanide, occur via the site-specific outer-sphere electron transfer mechanism, even though the same reagents oxidize structurally similar MbO 2 and cytochrome b 5 via the simple outer-sphere electron transfer mechanism. Of particular biological interest is HbO 2 and MbO 2 transformation into met-forms in the presence of small amounts of metal ions or complexes (catalysis), which, until recently, had been demonstrated only for copper compounds with intermediate redox potentials. The main contribution to the reaction rate comes from copper binding to the "inner" histidines, His97 (0.66 nm from the heme) that forms a hydrogen bond with the heme propionate COO - group, and the distal His64. The affinity of both histidines for copper is much lower than that of the surface histidines residues, and they are inaccessible for modification with chemical reagents. However, it was found recently that the high-potential Fe(3) complex, potassium ferricyanide (400 mV), at a 5 to 20% of molar protein concentration can be an efficient catalyst of MbO 2 oxidation into metMb. The catalytic process includes binding of ferrocyanide anion in the region of the His119 residue due to the presence there of a large positive local electrostatic potential and existence of a "pocket" formed by Lys16, Ala19, Asp20, and Arg118 that is sufficient to accommodate [Fe(CN) 6 ] 4- . Fast, proton-assisted reoxidation of the bound ferrocyanide by oxygen (which is required for completion of the catalytic cycle), unlike slow [Fe(CN) 6 ] 4- oxidation in solution, is provided by the optimal location of neighboring protonated His113 and His116, as it occurs in the enzyme active site.

Scavenging iron: a novel mechanism of plant immunity activation by microbial siderophores.

PubMed

Aznar, Aude; Chen, Nicolas W G; Rigault, Martine; Riache, Nassima; Joseph, Delphine; Desmaële, Didier; Mouille, Grégory; Boutet, Stéphanie; Soubigou-Taconnat, Ludivine; Renou, Jean-Pierre; Thomine, Sébastien; Expert, Dominique; Dellagi, Alia

2014-04-01

Siderophores are specific ferric iron chelators synthesized by virtually all microorganisms in response to iron deficiency. We have previously shown that they promote infection by the phytopathogenic enterobacteria Dickeya dadantii and Erwinia amylovora. Siderophores also have the ability to activate plant immunity. We have used complete Arabidopsis transcriptome microarrays to investigate the global transcriptional modifications in roots and leaves of Arabidopsis (Arabidopsis thaliana) plants after leaf treatment with the siderophore deferrioxamine (DFO). Physiological relevance of these transcriptional modifications was validated experimentally. Immunity and heavy-metal homeostasis were the major processes affected by DFO. These two physiological responses could be activated by a synthetic iron chelator ethylenediamine-di(o-hydroxyphenylacetic) acid, indicating that siderophores eliciting activities rely on their strong iron-chelating capacity. DFO was able to protect Arabidopsis against the pathogenic bacterium Pseudomonas syringae pv tomato DC3000. Siderophore treatment caused local modifications of iron distribution in leaf cells visible by ferrocyanide and diaminobenzidine-H₂O₂ staining. Metal quantifications showed that DFO causes a transient iron and zinc uptake at the root level, which is presumably mediated by the metal transporter iron regulated transporter1 (IRT1). Defense gene expression and callose deposition in response to DFO were compromised in an irt1 mutant. Consistently, plant susceptibility to D. dadantii was increased in the irt1 mutant. Our work shows that iron scavenging is a unique mechanism of immunity activation in plants. It highlights the strong relationship between heavy-metal homeostasis and immunity.

The Scope of Direct Alkylation of Gold Surface with Solutions of C1-C4 n-Alkylstannanes.

PubMed

Kaletová, Eva; Kohutová, Anna; Hajduch, Jan; Kaleta, Jiří; Bastl, Zdeněk; Pospíšil, Lubomír; Stibor, Ivan; Magnera, Thomas F; Michl, Josef

2015-09-23

Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin oxide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THF solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms.

Scavenging Iron: A Novel Mechanism of Plant Immunity Activation by Microbial Siderophores1[C][W

PubMed Central

Aznar, Aude; Chen, Nicolas W.G.; Rigault, Martine; Riache, Nassima; Joseph, Delphine; Desmaële, Didier; Mouille, Grégory; Boutet, Stéphanie; Soubigou-Taconnat, Ludivine; Renou, Jean-Pierre; Thomine, Sébastien; Expert, Dominique; Dellagi, Alia

2014-01-01

Siderophores are specific ferric iron chelators synthesized by virtually all microorganisms in response to iron deficiency. We have previously shown that they promote infection by the phytopathogenic enterobacteria Dickeya dadantii and Erwinia amylovora. Siderophores also have the ability to activate plant immunity. We have used complete Arabidopsis transcriptome microarrays to investigate the global transcriptional modifications in roots and leaves of Arabidopsis (Arabidopsis thaliana) plants after leaf treatment with the siderophore deferrioxamine (DFO). Physiological relevance of these transcriptional modifications was validated experimentally. Immunity and heavy-metal homeostasis were the major processes affected by DFO. These two physiological responses could be activated by a synthetic iron chelator ethylenediamine-di(o-hydroxyphenylacetic) acid, indicating that siderophores eliciting activities rely on their strong iron-chelating capacity. DFO was able to protect Arabidopsis against the pathogenic bacterium Pseudomonas syringae pv tomato DC3000. Siderophore treatment caused local modifications of iron distribution in leaf cells visible by ferrocyanide and diaminobenzidine-H2O2 staining. Metal quantifications showed that DFO causes a transient iron and zinc uptake at the root level, which is presumably mediated by the metal transporter iron regulated transporter1 (IRT1). Defense gene expression and callose deposition in response to DFO were compromised in an irt1 mutant. Consistently, plant susceptibility to D. dadantii was increased in the irt1 mutant. Our work shows that iron scavenging is a unique mechanism of immunity activation in plants. It highlights the strong relationship between heavy-metal homeostasis and immunity. PMID:24501001

Discovery and Characterization of a Pourbaix-Stable, 1.8 eV Direct Gap Bismuth Manganate Photoanode

DOE PAGES

Newhouse, Paul F.; Reyes-Lillo, Sebastian E.; Li, Guo; ...

2017-11-13

Solar-driven oxygen evolution is a critical technology for renewably synthesizing hydrogen- and carbon-containing fuels in solar fuel generators. New photoanode materials are needed to meet efficiency and stability requirements, motivating materials explorations for semiconductors with (i) band-gap energy in the visible spectrum and (ii) stable operation in aqueous electrolyte at the electrochemical potential needed to evolve oxygen from water. Motivated by the oxygen evolution competency of many Mn-based oxides, the existence of several Bi-containing ternary oxide photoanode materials, and the variety of known oxide materials combining these elements with Sm, we explore the Bi-Mn-Sm oxide system for new photoanodes. Throughmore » the use of a ferri/ferrocyanide redox couple in high-throughput screening, BiMn 2O 5 and its alloy with Sm are identified as photoanode materials with a near-ideal optical band gap of 1.8 eV. Using density functional theory-based calculations of the mullite Bi 3+ Mn 3+ Mn 4+O 5 phase, we identify electronic analogues to the well-known BiVO 4 photoanode and demonstrate excellent Pourbaix stability above the oxygen evolution Nernstian potential from pH 4.5 to 15. Lastly, our suite of experimental and computational characterization indicates that BiMn 2O 5 is a complex oxide with the necessary optical and chemical properties to be an efficient, stable solar fuel photoanode.« less

Discovery and Characterization of a Pourbaix-Stable, 1.8 eV Direct Gap Bismuth Manganate Photoanode

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

Newhouse, Paul F.; Reyes-Lillo, Sebastian E.; Li, Guo

Solar-driven oxygen evolution is a critical technology for renewably synthesizing hydrogen- and carbon-containing fuels in solar fuel generators. New photoanode materials are needed to meet efficiency and stability requirements, motivating materials explorations for semiconductors with (i) band-gap energy in the visible spectrum and (ii) stable operation in aqueous electrolyte at the electrochemical potential needed to evolve oxygen from water. Motivated by the oxygen evolution competency of many Mn-based oxides, the existence of several Bi-containing ternary oxide photoanode materials, and the variety of known oxide materials combining these elements with Sm, we explore the Bi-Mn-Sm oxide system for new photoanodes. Throughmore » the use of a ferri/ferrocyanide redox couple in high-throughput screening, BiMn 2O 5 and its alloy with Sm are identified as photoanode materials with a near-ideal optical band gap of 1.8 eV. Using density functional theory-based calculations of the mullite Bi 3+ Mn 3+ Mn 4+O 5 phase, we identify electronic analogues to the well-known BiVO 4 photoanode and demonstrate excellent Pourbaix stability above the oxygen evolution Nernstian potential from pH 4.5 to 15. Lastly, our suite of experimental and computational characterization indicates that BiMn 2O 5 is a complex oxide with the necessary optical and chemical properties to be an efficient, stable solar fuel photoanode.« less

Removal of cesium from simulated liquid waste with countercurrent two-stage adsorption followed by microfiltration.

PubMed

Han, Fei; Zhang, Guang-Hui; Gu, Ping

2012-07-30

Copper ferrocyanide (CuFC) was used as an adsorbent to remove cesium. Jar test results showed that the adsorption capacity of CuFC was better than that of potassium zinc hexacyanoferrate. Lab-scale tests were performed by an adsorption-microfiltration process, and the mean decontamination factor (DF) was 463 when the initial cesium concentration was 101.3μg/L, the dosage of CuFC was 40mg/L and the adsorption time was 20min. The cesium concentration in the effluent continuously decreased with the operation time, which indicated that the used adsorbent retained its adsorption capacity. To use this capacity, experiments on a countercurrent two-stage adsorption (CTA)-microfiltration (MF) process were carried out with CuFC adsorption combined with membrane separation. A calculation method for determining the cesium concentration in the effluent was given, and batch tests in a pressure cup were performed to verify the calculated method. The results showed that the experimental values fitted well with the calculated values in the CTA-MF process. The mean DF was 1123 when the dilution factor was 0.4, the initial cesium concentration was 98.75μg/L and the dosage of CuFC and adsorption time were the same as those used in the lab-scale test. The DF obtained by CTA-MF process was more than three times higher than the single-stage adsorption in the jar test. Copyright © 2012 Elsevier B.V. All rights reserved.

Pozzolanic filtration/solidification of radionuclides in nuclear reactor cooling water

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

Englehardt, J.D.; Peng, C.

1995-12-31

Laboratory studies to investigate the feasibility of one- and two-step processes for precipitation/coprecipitating radionuclides from nuclear reactor cooling water, filtering with pozzolanic filter aid, and solidifying, are reported in this paper. In the one-step process, ferrocyanide salt and excess lime are added ahead of the filter, and the resulting filter cake solidifies by a pozzolanic reaction. The two-step process involves addition of solidifying agents subsequent to filtration. It was found that high surface area diatomaceous synthetic calcium silicate powders, sold commercially as functional fillers and carriers, adsorb nickel isotopes from solution at neutral and slightly basic pH. Addition of themore » silicates to cooling water allowed removal of the tested metal isotopes (nickel, iron, manganese, cobalt, and cesium) simultaneously at neutral to slightly basic pH. Lime to diatomite ratio was the most influential characteristic of composition on final strength tested, with higher lime ratios giving higher strength. Diatomaceous earth filter aids manufactured without sodium fluxes exhibited higher pozzolanic activity. Pozzolanic filter cake solidified with sodium silicate and a ratio of 0.45 parts lime to 1 part diatomite had compressive strength ranging from 470 to 595 psi at a 90% confidence level. Leachability indices of all tested metals in the solidified waste were acceptable. In light of the typical requirement of removing iron and desirability of control over process pH, a two-step process involving addition of Portland cement to the filter cake may be most generally applicable.« less

Development of a Sensitive Electrochemical Enzymatic Reaction-Based Cholesterol Biosensor Using Nano-Sized Carbon Interdigitated Electrodes Decorated with Gold Nanoparticles

PubMed Central

Sharma, Deepti; Lee, Jongmin; Seo, Junyoung; Shin, Heungjoo

2017-01-01

We developed a versatile and highly sensitive biosensor platform. The platform is based on electrochemical-enzymatic redox cycling induced by selective enzyme immobilization on nano-sized carbon interdigitated electrodes (IDEs) decorated with gold nanoparticles (AuNPs). Without resorting to sophisticated nanofabrication technologies, we used batch wafer-level carbon microelectromechanical systems (C-MEMS) processes to fabricate 3D carbon IDEs reproducibly, simply, and cost effectively. In addition, AuNPs were selectively electrodeposited on specific carbon nanoelectrodes; the high surface-to-volume ratio and fast electron transfer ability of AuNPs enhanced the electrochemical signal across these carbon IDEs. Gold nanoparticle characteristics such as size and morphology were reproducibly controlled by modulating the step-potential and time period in the electrodeposition processes. To detect cholesterol selectively using AuNP/carbon IDEs, cholesterol oxidase (ChOx) was selectively immobilized via the electrochemical reduction of the diazonium cation. The sensitivity of the AuNP/carbon IDE-based biosensor was ensured by efficient amplification of the redox mediators, ferricyanide and ferrocyanide, between selectively immobilized enzyme sites and both of the combs of AuNP/carbon IDEs. The presented AuNP/carbon IDE-based cholesterol biosensor exhibited a wide sensing range (0.005–10 mM) and high sensitivity (~993.91 µA mM−1 cm−2; limit of detection (LOD) ~1.28 µM). In addition, the proposed cholesterol biosensor was found to be highly selective for the cholesterol detection. PMID:28914766

Comparative study of flux of FITC-labeled Dextran 4000 on normal (iso)- and hyper-osmolarity in basal side in caco-2 cell monolayers.

PubMed

Ohkubo, Rie; Tomita, Mikio; Hotta, Yoshiyuki; Nagira, Mayuko; Hayashi, Masahiro

2003-01-01

We have shown previously that the flux of fluorescein isothiocyanate dextran 4000 (FD-4) is transported across the Caco-2 cell monolayers in a polarized fashion favoring the basal to apical direction under normal conditions (i.e., isotonic solution in basal side). Furthermore, FD-4 transport may occur via a process that included a certain degree of substrate specificity for polysaccharide and transcytosis. In the present study, we compared the flux of FD-4 in the basal to apical direction (efflux) and the apical to basal direction (influx) in stress conditions (i.e., hyperosmolarity in basal side) to those in normal conditions (i.e., iso-osmolarity in basal side). The efflux of FD-4 was increased by hyperosmolarity in basal side, but the influx was decreased when compared with normal conditions. Neither dextran 10, 000 nor colchicine inhibited the efflux of FD-4 in hyperosmolarity conditions. The inhibition of efflux of FD-4 was observed not by S-nitroso-N-acetylpenicillamine but by sodium nitroprusside and sodium ferrocyanide. These results collectively suggest that hyperosmolarity in basal side accelerates the efflux of FD-4 across the transcellular route but not across the paracellular route in Caco-2 cell monolayers. And it is indicated that cyanide rather than nitric oxide is involved in dysfunction of the FD-4 efflux system irrespective of conditions such as normal osmolarity or hyperosmolarity.

Portable Lock-in Amplifier-Based Electrochemical Method to Measure an Array of 64 Sensors for Point-of-Care Applications.

PubMed

Hrdý, Radim; Kynclová, Hana; Klepáčová, Ivana; Bartošík, Martin; Neužil, Pavel

2017-09-05

We present a portable lock-in amplifier-based electrochemical sensing system. The basic unit (cluster) consists of four electrochemical cells (EC), each containing one pseudoreference electrode (PRE) and one working electrode (WE). All four ECs are simultaneously interrogated, each at different frequencies, with square wave pulses superposed on a sawtooth signal for cyclic voltammetry (CV). Lock-in amplification provides independent read-out of four signals, with excellent noise suppression. We expanded a single cluster system into an array of 16 clusters by using electronic switches. The chip with an array of ECs was fabricated using planar technology with a gap between a WE and a PRE of ≈2 μm, which results in partial microelectrode-type behavior. The basic electrode characterization was performed with the model case using a ferricyanide-ferrocyanide redox couple (Fe 2+ /Fe 3+ ) reaction, performing CV and differential pulse voltammetry (DPV). We then used this system to perform cyclic lock-in voltammetry (CLV) to measure concurrently responses of the four ECs. We repeated this method with all 64 ECs on the chip. The standard deviation of a peak oxidation and reduction current in a single channel consisting of 13 ECs was ≈7.46% and ≈5.6%, respectively. The four-EC configuration in each measured spot allows determination of nonperforming ECs and, thus, to eliminate potential false results. This system is built in a portable palm-size format suitable for point-of-care applications. It can perform either individual or multiple measurements of active compounds, such as biomarkers.

Single-Use Disposable Electrochemical Label-Free Immunosensor for Detection of Glycated Hemoglobin (HbA1c) Using Differential Pulse Voltammetry (DPV).

PubMed

Molazemhosseini, Alireza; Magagnin, Luca; Vena, Pasquale; Liu, Chung-Chiun

2016-07-01

A single-use disposable in vitro electrochemical immunosensor for the detection of HbA1c in undiluted human serum using differential pulse voltammetry (DPV) was developed. A three-electrode configuration electrochemical biosensor consisted of 10-nm-thin gold film working and counter electrodes and a thick-film printed Ag/AgCl reference electrode was fabricated on a polyethylene terephthalate (PET) substrate. Micro-fabrication techniques including sputtering vapor deposition and thick-film printing were used to fabricate the biosensor. This was a roll-to-roll cost-effective manufacturing process making the single-use disposable in vitro HbA1c biosensor a reality. Self-assembled monolayers of 3-Mercaptopropionic acid (MPA) were employed to covalently immobilize anti-HbA1c on the surface of gold electrodes. Electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) confirmed the excellent coverage of MPA-SAM and the upward orientation of carboxylic groups. The hindering effect of HbA1c on the ferricyanide/ferrocyanide electron transfer reaction was exploited as the HbA1c detection mechanism. The biosensor showed a linear range of 7.5-20 µg/mL of HbA1c in 0.1 M PBS. Using undiluted human serum as the test medium, the biosensor presented an excellent linear behavior (R² = 0.999) in the range of 0.1-0.25 mg/mL of HbA1c. The potential application of this biosensor for in vitro measurement of HbA1c for diabetic management was demonstrated.

Single-Use Disposable Electrochemical Label-Free Immunosensor for Detection of Glycated Hemoglobin (HbA1c) Using Differential Pulse Voltammetry (DPV)

PubMed Central

Molazemhosseini, Alireza; Magagnin, Luca; Vena, Pasquale; Liu, Chung-Chiun

2016-01-01

A single-use disposable in vitro electrochemical immunosensor for the detection of HbA1c in undiluted human serum using differential pulse voltammetry (DPV) was developed. A three-electrode configuration electrochemical biosensor consisted of 10-nm-thin gold film working and counter electrodes and a thick-film printed Ag/AgCl reference electrode was fabricated on a polyethylene terephthalate (PET) substrate. Micro-fabrication techniques including sputtering vapor deposition and thick-film printing were used to fabricate the biosensor. This was a roll-to-roll cost-effective manufacturing process making the single-use disposable in vitro HbA1c biosensor a reality. Self-assembled monolayers of 3-Mercaptopropionic acid (MPA) were employed to covalently immobilize anti-HbA1c on the surface of gold electrodes. Electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) confirmed the excellent coverage of MPA-SAM and the upward orientation of carboxylic groups. The hindering effect of HbA1c on the ferricyanide/ferrocyanide electron transfer reaction was exploited as the HbA1c detection mechanism. The biosensor showed a linear range of 7.5–20 µg/mL of HbA1c in 0.1 M PBS. Using undiluted human serum as the test medium, the biosensor presented an excellent linear behavior (R2 = 0.999) in the range of 0.1–0.25 mg/mL of HbA1c. The potential application of this biosensor for in vitro measurement of HbA1c for diabetic management was demonstrated. PMID:27376299

Spectroelectrochemical Sensors: New Polymer Films for Improved Sensitivity

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

Morris, Laura K.; Seliskar, Carl J.; Bryan, Samuel A.

2014-10-31

The selectivity of an optical sensor can be improved by combining optical detection with electrochemical oxidation or reduction of the target analyte to change its spectral properties. The changing signal can distinguish the analyte from interferences with similar spectral properties that would otherwise interfere. The analyte is detected by measuring the intensity of the electrochemically modulated signal. In one form this spectroelectrochemical sensor consists of an optically transparent electrode (OTE) coated with a film that preconcentrates the target analyte. The OTE functions as an optical waveguide for attenuated total reflectance (ATR) spectroscopy, which detects the analyte by absorption. Sensitivity reliesmore » in part on a large change in molar absorptivity between the two oxidation states used for electrochemical modulation of the optical signal. A critical part of the sensor is the ion selective film. It should preconcentrate the analyte and exclude some interferences. At the same time the film must not interfere with the electrochemistry or the optical detection. Therefore, since the debut of the sensor’s concept one major focus of our group has been developing appropriate films for different analytes. Here we report the development of a series of quaternized poly(vinylpyridine)-co-styrene (QPVP-co-S) anion exchange films for use in spectroelectrochemical sensors to enable sensitive detection of target anionic analytes in complex samples. The films were either 10% or 20% styrene and were prepared with varying degrees of quaternized pyridine groups, up to 70%. Films were characterized with respect to thickness with spectroscopic ellipsometry, degree of quaternization with FTIR, and electrochemically and spectroelectrochemically using the anions ferrocyanide and pertechnetate.« less

Plant cell nucleolus as a hot spot for iron.

PubMed

Roschzttardtz, Hannetz; Grillet, Louis; Isaure, Marie-Pierre; Conéjéro, Geneviève; Ortega, Richard; Curie, Catherine; Mari, Stéphane

2011-08-12

Many central metabolic processes require iron as a cofactor and take place in specific subcellular compartments such as the mitochondrion or the chloroplast. Proper iron allocation in the different organelles is thus critical to maintain cell function and integrity. To study the dynamics of iron distribution in plant cells, we have sought to identify the different intracellular iron pools by combining three complementary imaging approaches, histochemistry, micro particle-induced x-ray emission, and synchrotron radiation micro X-ray fluorescence. Pea (Pisum sativum) embryo was used as a model in this study because of its large cell size and high iron content. Histochemical staining with ferrocyanide and diaminobenzidine (Perls/diaminobenzidine) strongly labeled a unique structure in each cell, which co-labeled with the DNA fluorescent stain DAPI, thus corresponding to the nucleus. The unexpected presence of iron in the nucleus was confirmed by elemental imaging using micro particle-induced x-ray emission. X-ray fluorescence on cryo-sectioned embryos further established that, quantitatively, the iron concentration found in the nucleus was higher than in the expected iron-rich organelles such as plastids or vacuoles. Moreover, within the nucleus, iron was particularly accumulated in a subcompartment that was identified as the nucleolus as it was shown to transiently disassemble during cell division. Taken together, our data uncover an as yet unidentified although abundant iron pool in the cell, which is located in the nuclei of healthy, actively dividing plant tissues. This result paves the way for the discovery of a novel cellular function for iron related to nucleus/nucleolus-associated processes.

Minutes of the Tank Waste Science Panel Meeting March 25--27, 1992. Hanford Tank Safety Project

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

Schutz, W W; Consultant, Wellington, Delaware; Strachan, D M

Discussions from the seventh meeting of the Tank Waste Science are presented in Colorado. The subject areas included the generation of gases in Tank 241-SY-101, the possible use of sonication as a mitigation method, and analysis for organic constituents in core samples. Results presented and discussed include: Ferrocyanides appear to be rapidly dissolved in 1M NaOH; upon standing in the laboratory at ambient conditions oxalate precipitates from simulated wastes containing HEDTA. This suggests that one of the main components in the solids in Tank 241-SY-101 is oxalate; hydrogen evolved from waste samples from Tank 241-SY-101 is five times that observedmore » in the off gas from the tank; data suggest that mitigation of Tank 241-SY-101 will not cause a high release of dissolved N{sub 2}O; when using a slurry for radiation studies, a portion of the generated gases is very difficult to remove. To totally recover the generated gases, the solids must first be dissolved. This result may have an impact on mitigation by mixing if the gases are not released. Using {sup 13}C-labeled organics in thermal degradation studies has allowed researchers to illucidate much of the kinetic mechanism for the degradation of HEDTA and glycolate. In addition to some of the intermediate, more complex organic species, oxalate, formate, and CO{sub 2} were identified; and analytic methods for organics in radioactive complex solutions such as that found in Tank 241-SY-101 have been developed and others continue to be developed.« less

New solely Prussian-blue EC configurations

NASA Astrophysics Data System (ADS)

Rosseinsky, David R.; Soutar, Andrew M.; Annergren, Ingegerd F.; Glidle, Andrew

2001-11-01

The long-established ferric ferrocyanide chromophore Prussian Blue (PB) has often been studied for electrochromic use. New observations and conclusions are now presented. Detailed analyses, chemical and by means of EDX, of films deposited on Pt in a variety of conditions and solution compositions, are presented, and a remarkably efficient uptake of Cs+ noted. In particular, the pH for stablest film from KCl- containing solution should be high, ca 4-5. Details of the electrodeposition on ITO glass were examined, where earlier suppositions regarding the nature of the foundation layers are confirmed by direct observation. Unexpectedly, this is substantially of ferric-ferricyanide composition. The spectroscopic shifts of the intervalence charge-transfer absorption on incorporation of different univalent cations into PB are reported and analysed. The preparative precautions needed for deposition on larger (10 x 10 cm2) ITO glass electrodes are thoroughly examined. The electrochromic response of a dual-PB electrode setup in which one electrode can be switched to clear Prussian White and the other to the deep yellow of Prussian Yellow, presents an unlikely prospect for windows or other intensity-attenuation applications, but may serve e.g. in displays. In an alternative dual-PB array a metallic silver electrode is peripherally interposed, to act as a silver/silver- chloride counter electrode. The response time in the 10 x 10 cm2 system is approximately 90 s and is accompanied by a pronounced iris (racoon) effect. The assembly provides an interesting example of two-electrode operation of a larger (cf lab-scale) device. Two-electrode operation is discussed and clarified.

Electrochemical and microfabrication strategies for remotely operated smart chemical sensors: application of anodic stripping coulometry to calibration-free measurements of copper and mercury.

PubMed

Marei, Mohamed M; Roussel, Thomas J; Keynton, Robert S; Baldwin, Richard P

2013-11-25

Remote unattended sensor networks are increasingly sought after to monitor the drinking water distribution grid, industrial wastewater effluents, and even rivers and lakes. One of the biggest challenges for application of such sensors is the issue of in-field device calibration. With this challenge in mind, we report here the use of anodic stripping coulometry (ASC) as the basis of a calibration-free micro-fabricated electrochemical sensor (CF-MES) for heavy metal determinations. The sensor platform consisted of a photo-lithographically patterned gold working electrode on SiO2 substrate, which was housed within a custom stopped-flow thin-layer cell, with a total volume of 2-4 μL. The behavior of this platform was characterized by fluorescent particle microscopy and electrochemical studies utilizing Fe(CN)6(3-/4-) as a model analyte. The average charge obtained for oxidation of 500 μM ferrocyanide after 60s over a 10 month period was 176 μC, corresponding to a volume of 3.65 μL (RSD = 2.4%). The response of the platform to copper concentrations ranging from 50 to 7500 ppb was evaluated, and the ASC results showed a linear dependence of charge on copper concentrations with excellent reproducibility (RSD ≤ 2.5%) and accuracy for most concentrations (≤ 5-10% error). The platform was also used to determine copper and mercury mixtures, where the total metallic content was measurable with excellent reproducibility (RSD ≤ 4%) and accuracy (≤ 6% error). Copyright © 2013 Elsevier B.V. All rights reserved.

Interface proliferation and the growth of labyrinths in a reaction-diffusion system

NASA Astrophysics Data System (ADS)

Goldstein, Raymond E.; Muraki, David J.; Petrich, Dean M.

1996-04-01

In the bistable regime of the FitzHugh-Nagumo model of reaction-diffusion systems, spatially homogeneous patterns may be nonlinearly unstable to the formation of compact "localized states." The formation of space-filling patterns from instabilities of such structures is studied in the context of a nonlocal contour dynamics model for the evolution of boundaries between high and low concentrations of the activator. An earlier heuristic derivation [D. M. Petrich and R. E. Goldstein,

Anaerobic Killing of Oral Streptococci by Reduced, Transition Metal Cations

PubMed Central

Dunning, J. C.; Ma, Y.; Marquis, R. E.

1998-01-01

Reduced, transition metal cations commonly enhance oxidative damage to cells caused by hydroperoxides formed as a result of oxygen metabolism or added externally. As expected, the cations Fe2+ and Cu+ enhanced killing of Streptococcus mutans GS-5 by hydroperoxides. However, unexpectedly, they also induced lethal damage under fully anaerobic conditions in a glove box with no exposure to O2 or hydroperoxides from initial treatment with the cations. Sensitivities to anaerobic killing by Fe2+ varied among the organisms tested. The oral streptococci Streptococcus gordonii ATCC 10558, Streptococcus rattus FA-1, and Streptococcus sanguis NCTC 10904 were approximately as sensitive as S. mutans GS-5. Enterococcus hirae ATCC 9790, Actinomyces viscosus OMZ105E, and Actinomyces naeslundii WVU45 had intermediate sensitivity, while Lactobacillus casei ATCC 4646 and Escherichia coli B were insensitive. Killing of S. mutans GS-5 in response to millimolar levels of added Fe2+ occurred over a wide range of temperatures and pH. The organism was able to take up ferrous iron, but ferric reductase activity could not be detected. Chelators, uric acid, and thiocyanate were not effective inhibitors of the lethal damage. Sulfhydryl compounds, ferricyanide, and ferrocyanide were protective if added prior to Fe2+ exposure. Fe2+, but not Fe3+, acted to reduce the acid tolerance of glycolysis by intact cells of S. mutans. The reduction in acid tolerance appeared to be related directly to Fe2+ inhibition of F-ATPase, which could be assayed with permeabilized cells, isolated membranes, or F1 enzyme separated from membranes. Cu+ and Cu2+ also inhibited F-ATPase and sensitized glycolysis by intact cells to acid. All of these damaging actions occurred anaerobically and thus did not appear to involve reactive oxygen species. PMID:9435058

Nanostructured disposable impedimetric sensors as tools for specific biomolecular interactions: sensitive recognition of concanavalin A.

PubMed

Loaiza, Oscar A; Lamas-Ardisana, Pedro J; Jubete, Elena; Ochoteco, Estibalitz; Loinaz, Iraida; Cabañero, Germán; García, Isabel; Penadés, Soledad

2011-04-15

The development of sensors to detect specific weak biological interactions is still today a challenging topic. Characteristics of carbohydrate-protein (lectin) interactions include high specificity and low affinity. This work describes the development of nanostructured impedimetric sensors for the detection of concanavalin A (Con A) binding to immobilized thiolated carbohydrate derivatives (D-mannose or D-glucose) onto screen-printed carbon electrodes (SPCEs) modified with gold nanoparticles. Thiolated D-galactose derivative was employed as negative control to evaluate the selectivity of the proposed methodology. After binding the thiolated carbohydrate to the nanostructured SPCEs, different functionalized thiols were employed to form mixed self-assembled monolayers (SAM). Electrochemical impedance spectroscopy (EIS) was employed as a technique to evaluate the binding of Con A to selected carbohydrates through the increase of electron transfer resistance of the ferri/ferrocyanide redox probe at the differently SAM modified electrodes. Different variables of the assay protocol were studied in order to optimize the sensor performance. Selective Con A determinations were only achieved by the formation of mixed SAMs with adequate functionalized thiols. Important differences were obtained depending on the chain lengths and functional groups of these thiols. For the 3-mercapto-1-propanesulfonate mixed SAMs, the electron transfer resistance varied linearly with the Con A concentration in the 2.2-40.0 μg mL(-1) range for D-mannose and D-glucose modified sensors. Low detection limits (0.099 and 0.078 pmol) and good reproducibility (6.9 and 6.1%, n=10) were obtained for the D-glucose and D-mannose modified sensors, respectively, without any amplification strategy. © 2011 American Chemical Society

Fate of process solution cyanide and nitrate at three nevada gold mines inferred from stable carbon and nitrogen isotope measurements

USGS Publications Warehouse

Johnson, C.A.; Grimes, D.J.; Rye, R.O.

2000-01-01

Stable isotope methods have been used to identify the mechanisms responsible for cyanide consumption at three heap-leach operations that process Carlin-type gold ores in Nevada, U.S.A. The reagent cyanide had ??15N values ranging from -5 to -2??? and ??13C values from -60 to -35???. The wide ??13C range reflects the use by different suppliers of isotopically distinct natural-gas feedstocks and indicates that isotopes may be useful in environmental studies where there is a need to trace cyanide sources. In heap-leach circuits displaying from 5 to 98% consumption of cyanide, barren-solution and pregnant-solution cyanide were isotopically indistinguishable. The similarity is inconsistent with cyanide loss predominantly by HCN offgassing (a process that in laboratory experiments caused substantial isotopic changes), but it is consistent with cyanide retention within the heaps as solids, a process that caused minimal isotopic changes in laboratory simulations, or with cyanide oxidation, which also appears to cause minimal changes. In many pregnant solutions cyanide was carried entirely as metal complexes, which is consistent with ferrocyanides having precipitated or cyanocomplexes having been adsorbed within the heaps. It is inferred that gaseous cyanide emissions from operations of this type are less important than has generally been thought and that the dissolution or desorption kinetics of solid species is an important control on cyanide elution when the spent heaps undergo rinsing. Nitrate, nitrite and ammonium had ??15N values of 1-16???. The data reflect isotopic fractionation during ammonia offgassing or denitrification of nitrate - particularly in reclaim ponds - but do not indicate the extent to which nitrate is derived from cyanide or from explosive residues. ?? The Institution of Mining and Metallurgy 2000.

Graphene oxide electrochemistry: the electrochemistry of graphene oxide modified electrodes reveals coverage dependent beneficial electrocatalysis

PubMed Central

Smith, Graham C.

2017-01-01

The modification of electrode surfaces is widely implemented in order to try and improve electron transfer kinetics and surface interactions, most recently using graphene related materials. Currently, the use of ‘as is’ graphene oxide (GO) has been largely overlooked, with the vast majority of researchers choosing to reduce GO to graphene or use it as part of a composite electrode. In this paper, ‘as is’ GO is explored and electrochemically characterized using a range of electrochemical redox probes, namely potassium ferrocyanide(II), N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD), dopamine hydrochloride and epinephrine. Furthermore, the electroanalytical efficacy of GO is explored towards the sensing of dopamine hydrochloride and epinephrine via cyclic voltammetry. The electrochemical response of GO is benchmarked against pristine graphene and edge plane-/basal plane pyrolytic graphite (EPPG and BPPG respectively) alternatives, where the GO shows an enhanced electrochemical/electroanalytical response. When using GO as an electrode material, the electrochemical response of the analytes studied herein deviate from that expected and exhibit altered electrochemical responses. The oxygenated species encompassing GO strongly influence and dominate the observed voltammetry, which is crucially coverage dependent. GO electrocatalysis is observed, which is attributed to the presence of beneficial oxygenated species dictating the response in specific cases, demonstrating potential for advantageous electroanalysis to be realized. Note however, that crucial coverage based regions are observed at GO modified electrodes, owing to the synergy of edge plane sites and oxygenated species. We report the true beneficial electrochemistry of GO, which has enormous potential to be beneficially used in various electrochemical applications ‘as is’ rather than be simply used as a precursor to making graphene and is truly a fascinating member of the graphene family. PMID:29291099

Paper-based maskless enzymatic sensor for glucose determination combining ink and wire electrodes.

PubMed

Amor-Gutiérrez, O; Costa Rama, E; Costa-García, A; Fernández-Abedul, M T

2017-07-15

In this work we have developed an amperometric enzymatic biosensor in a paper-based platform with a mixed electrode configuration: carbon ink for the working electrode (WE) and metal wires (from a low-cost standard electronic connection) for reference (RE) and auxiliary electrodes (AE). A hydrophobic wax-defined paper area was impregnated with diluted carbon ink. Three gold-plated pins of the standard connection are employed, one for connecting the WE and the other two acting as RE and AE. The standard connection works as a clip in order to support the paper in between. As a proof-of-concept, glucose sensing was evaluated. The enzyme cocktail (glucose oxidase, horseradish peroxidase and potassium ferrocyanide as mediator of the electron transfer) was adsorbed on the surface. After drying, glucose solution was added to the paper, on the opposite side of the carbon ink. It wets RE and AE, and flows by capillarity through the paper contacting the carbon WE surface. The reduction current of ferricyanide, product of the enzymatic reaction, is measured chronoamperometrically and correlates to the concentration of glucose. Different parameters related to the bioassay were optimized, adhering the piece of paper onto a conventional screen-printed carbon electrode (SPCE). In this way, the RE and the AE of the commercial card were employed for optimizing the paper-WE. After evaluating the assay system in the hybrid paper-SPCE cell, the three-electrode system consisting of paper-WE, wire-RE and wire-AE, was employed for glucose determination, achieving a linear range between 0.3 and 15mM with good analytical features and being able of quantifying glucose in real food samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Chitosan coated on the layers' glucose oxidase immobilized on cysteamine/Au electrode for use as glucose biosensor.

PubMed

Zhang, Yawen; Li, Yunqiu; Wu, Wenjian; Jiang, Yuren; Hu, Biru

2014-10-15

A glucose biosensor was developed via direct immobilization of glucose oxidase (GOD) by self-assembled cysteamine monolayer on Au electrode surface followed by coating chitosan on the surface of electrode. In this work, chitosan film was coated on the surface of GOD as a protection film to ensure the stability and biocompatibility of the constructed glucose biosensor. The different application ranges of sensors were fabricated by immobilizing varied layers of GOD. The modified surface film was characterized by a scanning electron microscope (SEM) and the fabrication process of the biosensor was confirmed through electrochemical impedance spectroscopy (EIS) of ferrocyanide. The performance of cyclic voltammetry (CV) in the absence and presence of 25 mM glucose and ferrocenemethanol showed a diffusion-controlled electrode process and reflected the different maximum currents between the different GOD layers. With the developed glucose biosensor, the detection limits of the two linear responses are 49.96 μM and 316.8 μM with the sensitivities of 8.91 μA mM(-1)cm(-2) and 2.93 μA mM(-1)cm(-2), respectively. In addition, good stability (up to 30 days) of the developed biosensor was observed. The advantages of this new method for sensors construction was convenient and different width ranges of detection can be obtained by modified varied layers of GOD. The sensor with two layers of enzyme displayed two current linear responses of glucose. The present work provided a simplicity and novelty method for producing biosensors, which may help design enzyme reactors and biosensors in the future. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrocatalytic water treatment using carbon nanotube filters modified with metal oxides.

PubMed

Yang, So Young; Vecitis, Chad D; Park, Hyunwoong

2017-01-28

This study examined the electrocatalytic activity of multi-walled carbon nanotube (CNT) filters for remediation of aqueous phenol in a sodium sulfate electrolyte. CNT filters were loaded with antimony-doped tin oxide (Sb-SnO 2 ; SS) and bismuth- and antimony-codoped tin oxide (Bi-Sb-SnO 2 ; BSS) via electrosorption at 2 V for 1 h and then assembled into a flow-through batch reactor as anode-cathode couples with perforated titanium foils. The as-synthesized pristine CNT filters were composed of 50-60-nm-thick tubular carbons with smooth surfaces, whereas the tubes composing the SS-CNT and BSS-CNT filters were slightly thicker and bumpy, because they were coated with SS and BSS particles ~50 nm in size. Electrochemical characterization of the samples indicated a positive shift in the onset potential and a decrease in the current magnitude in the modified CNT filters due to passivation and oxidation inhibition of the bare CNT filters. These filters exhibited a similar adsorption capacity for phenol (5-8%), whereas loadings of SS and BSS enhanced the degradation rate of phenol by ~1.5 and 2.1 times, respectively. In particular, the total organic carbon removal performance and mineralization efficiency of the BSS-CNT filters were approximately twice those of the bare CNT filters. The BSS-CNT filters also exhibited an enhanced oxidation of ferrocyanide [Fe II (CN) 6 4- ], which was not adsorbed onto the CNT filters. The enhanced electrocatalytic performance of the modified CNT filters was attributed to an effective generation of OH radicals. The surfaces of the filters were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy.

Lubiprostone stimulates duodenal bicarbonate secretion in rats.

PubMed

Mizumori, Misa; Akiba, Yasutada; Kaunitz, Jonathan D

2009-10-01

Lubiprostone, a bicyclic fatty acid, is used for the treatment of chronic constipation. No published study has addressed the effect of lubiprostone on intestinal ion secretion in vivo. The aim of this study was to test the hypothesis that lubiprostone augments duodenal HCO(3) (-) secretion (DBS). Rat proximal duodenal loops were perfused with pH 7.0 Krebs, control vehicle (medium-chain triglycerides), or lubiprostone (0.1-10 microM). We measured DBS with flow-through pH and CO(2) electrodes, perfusate [Cl(-)] with a Cl(-) electrode, and water flux using a non-absorbable ferrocyanide marker. Some rats were pretreated with a potent, selective CFTR antagonist, CFTR(inh)-172 (1 mg/kg, ip), 1 h before experiments. Perfusion of lubiprostone concentration dependently increased DBS, whereas net Cl(-) output and net water output were only increased at 0.1 microM, compared with vehicle. CFTR(inh)-172 reduced lubiprostone (10 microM)-induced DBS increase, whereas net Cl(-) output was also unchanged. Nevertheless, CFTR(inh)-172 reduced basal net water output, which was reversed by lubiprostone. Furthermore, lubiprostone-induced DBS was inhibited by EP4 receptor antagonist, not by an EP1/2 receptor antagonist or by indomethacin pretreatment. In this first study of the effect of lubiprostone on intestinal ion secretion in vivo, lubiprostone stimulated CFTR-dependent DBS without changing net Cl(-) secretion. This effect supports the hypothesis that Cl(-) secreted by CFTR is recycled across the apical membrane by anion exchangers. Recovery of water output during CFTR inhibition suggests that lubiprostone may improve the intestinal phenotype in CF patients. Furthermore, increased DBS suggests that lubiprostone may protect the duodenum from acid-induced injury via EP4 receptor activation.

Effects of a fire-retardant chemical to fathead minnows in experimental streams

USGS Publications Warehouse

Calfee, R.D.; Little, E.E.

2003-01-01

Background. Each year millions of liters of fire-retardant chemicals are applied to wildfires across the nation. Recent laboratory studies with long-term fire-retardant chemicals indicate a significant photoenhanced toxicity of products containing sodium ferrocyanide corrosion inhibitors. Our objective of this study was to determine the toxicity of fire-retardant chemicals to fathead minnows during exposure in experimental outdoor streams. Methods. Stream tests were conducted to determine the potential toxicity of a pulse of exposure as might occur when fire retardant chemical is rinsed from the watershed by rainfall. Two artificial 55-meter experimental streams were dosed with different concentrations of Fire-Trol?? GTS-R, or uncontaminated for a control. Replicate groups of fathead minnows were added to screened containers (10 fish per container) and exposed to retardant chemicals in the recirculating flow of the stream for up to 6 hours. Results and Discussion. Under field conditions toxicity of GTS-R only occurred in the presence of sunlight. When GTS-R was tested on sunny days, 100% mortality occurred. However, when tested during heavily overcast conditions, no mortality occurred. Conclusions. Lethal concentrations of cyanide were measured when GTS-R with YPS exposures were conducted under sunny conditions, but not under cloudy conditions, indicating that a minimum UV level is necessary to induce toxicity as well as the release of cyanide from YPS. The toxicity observed with GTS-R was likely associated with lethal concentrations of cyanide. Rainwater runoff following applications of this fire-retardant at the recommended rate could result in lethal concentrations in small ponds and streams receiving limited water flow under sunny conditions. Recommendations and Outlook. In addition to avoiding application to aquatic habitats, it is important to consider characteristics of the treated site including soil binding affinity and erosive properties.

Nitric oxide contributes to minerals absorption, proton pumps and hormone equilibrium under cadmium excess in Trifolium repens L. plants.

PubMed

Liu, Shiliang; Yang, Rongjie; Pan, Yuanzhi; Ma, Mingdong; Pan, Jiang; Zhao, Yan; Cheng, Qingsu; Wu, Mengxi; Wang, Maohua; Zhang, Lin

2015-09-01

Nitric oxide (NO) is a stress-signaling molecule in plants that mediates a wide range of physiological processes and responses to metal toxicity. In this work, various NO modulators (NO donor: SNP; NO scavenger: cPTIO; NO synthase inhibitor: l-NAME; and SNP analogs: sodium nitrite/nitrate and sodium ferrocyanide) were investigated to determine the role of NO in Trifolium repens L. plants exposed to Cd. Cd (100μM) markedly reduced biomass, NO production and chlorophyll (Chl a, Chl b and total Chl) concentration but stimulated reactive oxygen species (ROS) and Cd accumulation in plants. SNP (50μM) substantially attenuated growth inhibition, reduced hydrogen peroxide (H2O2) and malonyldialdehyde (MDA) levels, stimulated ROS-scavenging enzymes/agents, and mitigated the H(+)-ATPase inhibition in proton pumps. Interestingly, SNP considerably up-regulated the levels of jasmonic acid (JA) and proline in plant tissues but down-regulated the levels of ethylene (ET) in both shoots and roots and the level of salicylic acid (SA) in roots only, which might be related to the elevated NO synthesis. Additionally, SNP (25-200μM) regulated mineral absorption and, particularly at 50μM, significantly enhanced the uptake of shoot magnesium (Mg) and copper (Cu) and of root calcium (Ca), Mg and iron (Fe). Nevertheless, the effects of SNP on plant growth were reversed by cPTIO and l-NAME, suggesting that the protective effect of SNP might be associated with NO synthesis in vivo. Moreover, SNP analogs did not display roles similar to that of SNP. These results indicated that NO depleted Cd toxicity by eliminating oxidative damage, enhancing minerals absorption, regulating proton pumps, and maintaining hormone equilibrium. Copyright © 2015 Elsevier Inc. All rights reserved.

Fabrication of nanofibers reinforced polymer microstructures using femtosecond laser material processing

NASA Astrophysics Data System (ADS)

Alubaidy, Mohammed-Amin

A new method has been introduced for the formation of microfeatures made of nanofibers reinforced polymer, using femtosecond laser material processing. The Femtosecond laser is used for the generation of three-dimensional interweaved nanofibers and the construction of microfeatures, like microchannels and voxels, through multi photon polymerization of nanofiber dispersed polymer resin. A new phenomenon of multiphoton polymerization induced by dual wavelength irradiation was reported for the first time. A significant improvement in the spatial resolution, compared to the two photon absorption (2PA) and the three photon absorption (3PA) processes has been achieved. Conductive polymer microstructures and magnetic polymer microstructures have been fabricated through this method. The mechanical properties of nanofiber reinforced polymer microstructures has been investigated by means of nanoindentation and the volume fraction of the generated nanofibers in the nanocomposite was calculated by using nanoindentation analysis. The results showed significant improvement in strength of the material. The electrical conductivity of the two photon polymerization (TPP) generated microfeatures was measured by a two-probe system at room temperature and the conductivity-temperature relationship was measured at a certain temperature range. The results suggest that the conductive polymer microstructure is reproducible and has a consistent conductivity-temperature relation. The magnetic strength has been characterized using Guassmeter. To demonstrate the potential application of the new fabrication method, a novel class of DNA-functionalized three-dimensional (3D), stand-free, and nanostructured electrodes were fabricated. The developed nanofibrous DNA biosensor has been characterized by cyclic voltammetry with the use of ferrocyanide as an electrochemical redox indicator. Results showed that the probe--target recognition has been improved. This research demonstrated that femtosecond laser materials processing is a viable tool of the construction of naomaterial- reinforced polymer microfeatures with tailored properties.

Charge-transfer interactions of Cr species with DNA.

PubMed

Nowicka, Anna M; Matysiak-Brynda, Edyta; Hepel, Maria

2017-10-01

Interactions of Cr species with nucleic acids in living organisms depend strongly on Cr oxidation state and the environmental conditions. As the effects of these interactions range from benign to pre-mutagenic to carcinogenic, careful assessment of the hazard they pose to human health is necessary. We have investigated methods that would enable quantifying the DNA damage caused by Cr species under varying environmental conditions, including UV, O 2 , and redox potential, using simple instrumental techniques which could be in future combined into a field-deployable instrumentation. We have employed electrochemical quartz crystal nanogravimetry (EQCN), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) to evaluate the extent of DNA damage expressed in terms of guanine oxidation yield (η) and changes in specific characteristics provided by these techniques. The effects of the interactions of Cr species with DNA were analyzed using a model calf thymus DNA (ctDNA) film on a gold electrode (Au@ctDNA) in different media, including: (i) Cr(VI), (ii) Cr(VI) reduced at -0.2V, (iii) Cr(III)+UV radiation+O 2 , and Cr(III), obtaining the η values: 7.4±1.4, 1.5±0.4, 1.1±0.31%, and 0%, respectively, thus quantifying the hazard posed. The EIS measurements have enabled utilizing the decrease in charge-transfer resistance (R ct ) for ferri/ferrocyanide redox probe at an Au@ctDNA electrode to assess the oxidative ctDNA damage by Cr(VI) species. In this case, circular dichroism indicates an extensive damage to the ctDNA hydrogen bonding. On the other hand, Cr(III) species have not induced any damage to ctDNA, although the EQCN measurements show an electrostatic binding to DNA. Copyright © 2017 Elsevier Inc. All rights reserved.

Exogenous NO depletes Cd-induced toxicity by eliminating oxidative damage, re-establishing ATPase activity, and maintaining stress-related hormone equilibrium in white clover plants.

PubMed

Liu, S L; Yang, R J; Pan, Y Z; Wang, M H; Zhao, Y; Wu, M X; Hu, J; Zhang, L L; Ma, M D

2015-11-01

Various nitric oxide (NO) regulators [including the NO donor sodium nitroprusside (SNP), the NO scavenger 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (cPTIO), the NO-synthase inhibitor N (G)-nitro-L-Arg-methyl ester (L-NAME), and the SNP analogues sodium nitrite/nitrate and sodium ferrocyanide] were investigated to elucidate the role of NO in white clover (Trifolium repens L.) plants after long-term (5 days) exposure to cadmium (Cd). A dose of 100 μM Cd stress significantly restrained plant growth and decreased the concentrations of chlorophyll and NO in vivo, whereas it disrupted the balance of stress-related hormones and enhanced the accumulation of Cd, thereby inducing reactive oxygen species (ROS) burst. However, the inhibition of plant growth was relieved by 50 μM SNP through its stimulation of ROS-scavenging compounds (ascorbic acid, ascorbate peroxidase, catalase, glutathione reductase, non-protein thiol, superoxide dismutase, and total glutathione), regulation of H(+)-ATPase activity of proton pumps, and increasing jasmonic acid and proline but decreasing ethylene in plant tissues. Even so, the alleviating effect of SNP on plant growth was counteracted by cPTIO and L-NAME and was not observed with SNP analogues, suggesting that the protective roles of SNP are related to the induction of NO. These results suggest that NO may improve the Cd tolerance of white clover plants by eliminating oxidative damage, re-establishing ATPase activity, and maintaining hormone equilibrium. Improving our understanding of the role of NO in white clover plants is key to expanding the plantations to various regions and the recovery of pasture species in the future.

Simultaneous fluorescence light-up and selective multicolor nucleobase recognition based on sequence-dependent strong binding of berberine to DNA abasic site.

PubMed

Wu, Fei; Shao, Yong; Ma, Kun; Cui, Qinghua; Liu, Guiying; Xu, Shujuan

2012-04-28

Label-free DNA nucleobase recognition by fluorescent small molecules has received much attention due to its simplicity in mutation identification and drug screening. However, sequence-dependent fluorescence light-up nucleobase recognition and multicolor emission with individual emission energy for individual nucleobases have been seldom realized. Herein, an abasic site (AP site) in a DNA duplex was employed as a binding field for berberine, one of isoquinoline alkaloids. Unlike weak binding of berberine to the fully matched DNAs without the AP site, strong binding of berberine to the AP site occurs and the berberine's fluorescence light-up behaviors are highly dependent on the target nucleobases opposite the AP site in which the targets thymine and cytosine produce dual emission bands, while the targets guanine and adenine only give a single emission band. Furthermore, more intense emissions are observed for the target pyrimidines than purines. The flanking bases of the AP site also produce some modifications of the berberine's emission behavior. The binding selectivity of berberine at the AP site is also confirmed by measurements of fluorescence resonance energy transfer, excited-state lifetime, DNA melting and fluorescence quenching by ferrocyanide and sodium chloride. It is expected that the target pyrimidines cause berberine to be stacked well within DNA base pairs near the AP site, which results in a strong resonance coupling of the electronic transitions to the particular vibration mode to produce the dual emissions. The fluorescent signal-on and emission energy-modulated sensing for nucleobases based on this fluorophore is substantially advantageous over the previously used fluorophores. We expect that this approach will be developed as a practical device for differentiating pyrimidines from purines by positioning an AP site toward a target that is available for readout by this alkaloid probe. This journal is © The Royal Society of Chemistry 2012

Electric field effects on current–voltage relationships in microfluidic channels presenting multiple working electrodes in the weak-coupling limit

DOE PAGES

Contento, Nicholas M.; Bohn, Paul W.

2014-05-23

While electrochemical methods are well suited for lab-on-a-chip applications, reliably coupling multiple, electrode-controlled processes in a single microfluidic channel remains a considerable challenge, because the electric fields driving electrokinetic flow make it difficult to establish a precisely known potential at the working electrode(s). The challenge of coupling electrochemical detection with microchip electrophoresis is well known; however, the problem is general, arising in other multielectrode arrangements with applications in enhanced detection and chemical processing. Here, we study the effects of induced electric fields on voltammetric behavior in a microchannel containing multiple in-channel electrodes, using a Fe(CN) 6 3/4- model system. Whenmore » an electric field is induced by applying a cathodic potential at one inchannel electrode, the half-wave potential (E 1/2) for the oxidation of ferrocyanide at an adjacent electrode shifts to more negative potentials. The E 1/2 value depends linearly on the electric field current at a separate in-channel electrode. The observed shift in E 1/2 is quantitatively described by a model, which accounts for the change in solution potential caused by the iR drop along the length of the microchannel. The model, which reliably captures changes in electrode location and solution conductivity, apportions the electric field potential between iR drop and electrochemical potential components, enabling the study of microchannel electric field magnitudes at low applied potentials. In the system studied, the iR component of the electric field potential increases exponentially with applied current before reaching an asymptotic value near 80 % of the total applied potential. The methods described will aid in the development and interpretation of future microchip electrochemistry methods, particularly those that benefit from the coupling of electrokinetic and electrochemical phenomena at low voltages.« less

Trehalose protects Mn-depleted photosystem 2 preparations against the donor-side photoinhibition.

PubMed

Yanykin, D V; Khorobrykh, A A; Mamedov, M D; Klimov, V V

2016-11-01

Recently, it has been shown that the addition of 1M trehalose leads to the increase of the rate of oxygen photoconsumption associated with activation of electron transport in the reaction center of photosystem 2 (PS2) in Mn-depleted PS2 membranes (apo-WOC-PS2) [37]. In the present work the effect of trehalose on photoinhibition of apo-WOC-PS2 preparations (which are characterized by a high sensitivity to the donor side photoinhibition of PS2) was investigated. The degree of photoinhibition was estimated by the loss of the capability of exogenous electron donor (sodium ascorbate) to reactivate the electron transport (measured by light-induced changes of chlorophyll fluorescence yield (∆F)) in apo-WOC-PS2. It was found that 1M trehalose enhanced the Mn 2+ -dependent suppression of photoinhibition of apo-WOC-PS2: in the presence of trehalose the addition of 0.2μM Mn 2+ (corresponding to 2 Mn 2+ per one reaction center) was sufficient for an almost complete suppression of the donor side photoinhibition of the complex. In the absence of trehalose it was necessary to add 100μM Mn 2+ to achieve a similar result. The effect of trehalose was observed during photoinhibition of apo-WOC-PS2 at low (15μmolphotons -1 m -2 ) and high (200μmolphotons -1 m -2 ) light intensity. When Mn 2+ was replaced by other PS2 electron donors (ferrocyanide, DPC) as well as by Ca 2+ the protective effect of trehalose was not observed. It was also found that 1M trehalose decreased photoinhibition of apo-WOC-PS2 if the samples contained endogenous manganese (1-2 Mn ions per one RC was enough for the maximum protection effect). It is concluded that structural changes in PS2 caused by the addition of trehalose enhance the capability of photochemical reaction centers of apo-WOC-PS2 to accept electrons from manganese (both exogenous and endogenous), which in turn leads to a considerable suppression of the donor side photoinhibition of PS2. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of thick mesoporous gamma-alumina films, loading of Pt nanoparticles, and use of the composite film as a reusable catalyst.

PubMed

Dandapat, Anirban; Jana, Debrina; De, Goutam

2009-04-01

Nanocrystalline mesoporous gamma-Al2O3 film of high thickness has been developed and characterized. The films were prepared on ordinary glass substrates by a single dip-coating method using boehmite (AlOOH) sols derived from aluminum tri-sec-butoxide in presence of cetyltrimethylammonium bromide (CTAB) as structure-directing agent. The dried films were heat-treated at 500 degrees C in air to remove the organics and strengthen the network. The GIXRD of the heat-treated (500 degrees C) film shows a broad peak in the low-angle region supporting the formation of worm-hole-like disordered mesostructures. The high-angle GIXRD, FTIR, and TEM of the films confirm the formation of gamma-Al2O3. N2 adsorption-desorption analyses showed that the heat-treated (500 degrees C) film has a BET surface area of 171 m(2) g(-1) with a pore volume of 0.188 cm(3) g(-1) and mean pore diameter 4.3 nm. Pt nanoparticles (NPs) (approximately 2.7 mol % with respect to the equivalent AlO(1.5)) were generated inside the mesopores of the heat-treated films simply by soaking H2PtCl6 solutions into it, and followed by thermal decomposition at 500 degrees C. The surface area and pore volume of the Pt-incorporated film have been reduced to 101 m(2) g(-1) and 0.119 cm(3) g(-1) respectively, confirming the inclusion of Pt NPs inside the pores. FESEM and TEM studies revealed uniform distribution of Pt NPs (2-8.5 nm; average diameter 4.9 nm) in the films. Catalytic properties of the Pt-incorporated films were investigated in two model (one inorganic and other organic) systems: reduction of hexacyanoferrate(III) ions by thiosulfate to ferrocyanide, and p-nitrophenol to p-aminophenol. In both the cases, the catalyst showed excellent activities, and the reduction reactions followed smoothly, showing isosbestic points in the UV-visible spectra. The catalyst films can be separated easily after the reactions and reused several times.

Metal-ligand Covalency of Iron Complexes from High-Resolution Resonant Inelastic X-ray Scattering

PubMed Central

Lundberg, Marcus; Kroll, Thomas; DeBeer, Serena; Bergmann, Uwe; Wilson, Samuel A.; Glatzel, Pieter; Nordlund, Dennis; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

2013-01-01

Data from Kα resonant inelastic X-ray scattering (RIXS) have been used to extract electronic structure information, i.e., the covalency of metal-ligand bonds, for four iron complexes using an experimentally based theoretical model. Kα RIXS involves resonant 1s → 3d excitation and detection of the 2p → 1s (Kα) emission. This two-photon process reaches similar final states as single-photon L-edge (2p → 3d) X-ray absorption spectroscopy (XAS), but involves only hard X-rays and can therefore be used to get high-resolution L-edge-like spectra for metal proteins, solution catalysts and their intermediates. To analyze the information content of Kα RIXS spectra, data have been collected for four characteristic σ-donor and π-backdonation complexes; ferrous tacn [FeII(tacn)2]Br2, ferrocyanide [FeII(CN)6]K4, ferric tacn [FeIII(tacn)2]Br3 and ferricyanide [FeIII(CN)6]K3. From these spectra metal-ligand covalencies can be extracted using a charge-transfer multiplet model, without previous information from the L-edge XAS experiment. A direct comparison of L-edge XAS and Kα RIXS spectra show that the latter reaches additional final states, e.g., when exciting into the eg (σ*) orbitals, and the splitting between final states of different symmetry provides an extra dimension that makes Kα RIXS a more sensitive probe of σ-bonding. Another key difference between L-edge XAS and Kα RIXS is the π-backbonding features in ferro- and ferricyanide that are significantly more intense in L-edge XAS compared to Kα RIXS. This shows that two methods are complimentary in assigning electronic structure. The Kα RIXS approach can thus be used as a stand-alone method, in combination with L-edge XAS for strongly covalent systems that are difficult to probe by UV/Vis spectroscopy, or as an extension to conventional absorption spectroscopy for a wide range of transition metal enzymes and catalysts. PMID:24131028

Complexes with Tunable Intramolecular Ferrocene to Ti(IV) Electronic Transitions: Models for Solid State Fe(II) to Ti(IV) Charge Transfer.

PubMed

Turlington, Michael D; Pienkos, Jared A; Carlton, Elizabeth S; Wroblewski, Karlee N; Myers, Alexis R; Trindle, Carl O; Altun, Zikri; Rack, Jeffrey J; Wagenknecht, Paul S

2016-03-07

Iron(II)-to-titanium(IV) metal-to-metal-charge transfer (MMCT) is important in the photosensitization of TiO2 by ferrocyanide, charge transfer in solid-state metal-oxide photocatalysts, and has been invoked to explain the blue color of sapphire, blue kyanite, and some lunar material. Herein, a series of complexes with alkynyl linkages between ferrocene (Fc) and Ti(IV) has been prepared and characterized by UV-vis spectroscopy and electrochemistry. Complexes with two ferrocene substituents include Cp2Ti(C2Fc)2, Cp*2Ti(C2Fc)2, and Cp2Ti(C4Fc)2. Complexes with a single ferrocene utilize a titanocene with a trimethylsilyl derivatized Cp ring, (TMS)Cp, and comprise the complexes (TMS)Cp2Ti(C2Fc)(C2R), where R = C6H5, p-C6H4CF3, and CF3. The complexes are compared to Cp2Ti(C2Ph)2, which lacks the second metal. Cyclic voltammetry for all complexes reveals a reversible Ti(IV/III) reduction wave and an Fe(II/III) oxidation that is irreversible for all complexes except (TMS)Cp2Ti(C2Fc)(C2CF3). All of the complexes with both Fc and Ti show an intense absorption (4000 M(-1)cm(-1) < ε < 8000 M(-1)cm(-1)) between 540 and 630 nm that is absent in complexes lacking a ferrocene donor. The energy of the absorption tracks with the difference between the Ti(IV/III) and Fe(III/II) reduction potentials, shifting to lower energy as the difference in potentials decreases. Reorganization energies, λ, have been determined using band shape analysis (2600 cm(-1) < λ < 5300 cm(-1)) and are in the range observed for other donor-acceptor complexes that have a ferrocene donor. Marcus-Hush-type analysis of the electrochemical and spectroscopic data are consistent with the assignment of the low-energy absorption as a MMCT band. TD-DFT analysis also supports this assignment. Solvatochromism is apparent for the MMCT band of all complexes, there being a bathochromic shift upon increasing polarizability of the solvent. The magnitude of the shift is dependent on both the electron density at Ti(IV) and the identity of the linker between the titanocene and the Fc. Complexes with a MMCT are photochemically stable, whereas Cp2Ti(C2Ph)2 rapidly decomposes upon photolysis.

Iron and gallium increase iron uptake from transferrin by human melanoma cells: further examination of the ferric ammonium citrate-activated iron uptake process.

PubMed

Richardson, D R

2001-04-30

Previously we showed that preincubation of cells with ferric ammonium citrate (FAC) resulted in a marked increase in Fe uptake from both (59)Fe-transferrin (Tf) and (59)Fe-citrate (D.R. Richardson, E. Baker, J. Biol. Chem. 267 (1992) 13972-13979; D.R. Richardson, P. Ponka, Biochim. Biophys. Acta 1269 (1995) 105-114). This Fe uptake process was independent of the transferrin receptor and appeared to be activated by free radicals generated via the iron-catalysed Haber-Weiss reaction. To further understand this process, the present investigation was performed. In these experiments, cells were preincubated for 3 h at 37 degrees C with FAC or metal ion solutions and then labelled for 3 h at 37 degrees C with (59)Fe-Tf. Exposure of cells to FAC resulted in Fe uptake from (59)Fe-citrate that became saturated at an Fe concentration of 2.5 microM, while FAC-activated Fe uptake from Tf was not saturable up to 25 microM. In addition, the extent of FAC-activated Fe uptake from citrate was far greater than that from Tf. These results suggest a mechanism where FAC-activated Fe uptake from citrate may result from direct interaction with the transporter, while Fe uptake from Tf appears indirect and less efficient. Preincubation of cells with FAC at 4 degrees C instead of 37 degrees C prevented its effect at stimulating (59)Fe uptake from (59)Fe-Tf, suggesting that an active process was involved. Previous studies by others have shown that FAC can increase ferrireductase activity that may enhance (59)Fe uptake from (59)Fe-Tf. However, there was no difference in the ability of FAC-treated cells compared to controls to reduce ferricyanide to ferrocyanide, suggesting no change in oxidoreductase activity. To examine if activation of this Fe uptake mechanism could occur by incubation with a range of metal ions, cells were preincubated with either FAC, ferric chloride, ferrous sulphate, ferrous ammonium sulphate, gallium nitrate, copper chloride, zinc chloride, or cobalt chloride. Stimulation of (59)Fe uptake from Tf was shown (in order of potency) with ferric chloride, ferrous sulphate, ferrous ammonium sulphate, and gallium nitrate. The other metal ions examined decreased (59)Fe uptake from Tf. The fact that redox-active Cu(II) ion did not stimulate Fe uptake while redox-inactive Ga(III) did, suggests a mechanism of transporter activation not solely dependent on free radical generation. Indeed, the activation of Fe uptake appears dependent on the presence of the Fe atom itself or a metal ion with atomic similarities to Fe (e.g. Ga).

Effects of anions and cations on the resting membrane potential of internally perfused barnacle muscle fibres

PubMed Central

Lakshminarayanaiah, N.; Rojas, E.

1973-01-01

1. Single barnacle muscle fibres from Megabalanus psittacus (Darwin) were internally perfused with a number of K salt solutions (200 mM) which were made isotonic to the barnacle saline with sucrose. 2. 200 mM-K acetate solution, in general, was found to be more effective than other solutions of K salts in generating and maintaining stable resting membrane potential of -56·0 ± 0·7 mV (all potentials are referred to the external solutions as ground). The various K salts, on the basis of the magnitude of the resting potential they generated in the muscle fibres, followed the sequence, acetate > isethionate > aspartate > glutamate > fluoride > monohydrogen phosphate > succinate > citrate > sulphate > oxalate > iodobenzoate > ferrocyanide > chlorate > nitrate > chloride > thiocyanate > iodide > bromide > cyanide. 3. The resting potential in muscle fibres perfused with solutions of acetate, aspartate and glutamate increased linearly with the logarithm of the K concentration (slope = 30·4 mV for K acetate and 27·4 for K aspartate and glutamate) when the ionic strength of the solutions was progressively increased from 50 to 650 mM. On the other hand, similar increase of ionic strength beyond 200 mM of solutions of K isethionate, fluoride, monohydrogen phosphate, succinate and citrate depolarized the muscle fibres. 4. Perfusion of acetate solutions of other alkali metal ions gave low values for the resting potential and followed the sequence K > Na > Rb > Li > Cs. Also NH4 and Tris ions gave low values for the resting potential which underwent oscillations associated with the twitching of the fibre and occasionally became positive in value (action potential). 5. Addition of tetraethyl ammonium chloride (TEA-Cl), 20-100 mM, to K acetate solutions (200 mM) depolarized the fibre membrane and the consequent reduction of resting potential varied linearly with the logarithm of TEA concentration. 6. Replacement of chloride ion by acetate or isethionate in the external solution did not change significantly the resting potential although the values were consistently lower by about 2 mV. 7. Complete elimination of K in the external solution and reduction of its ionic strength using sucrose depolarized the muscle fibres by about 27 mV when Na was changed from 475 to 1 mM. Under these conditions, external solutions completely in acetate form gave resting potentials which were more positive than those observed in completely chloride solutions by 6-8 mV. 8. Replacement of Na by Li, Tris, choline, tetramethyl or tetraethyl ammonium ion in the external solution made the values of the resting potential more positive (depolarization). Similarly increasing the concentration of K (or Cs or Rb in place of K) by correspondingly decreasing the concentration of Na in the outside solution depolarized the fibres and the resting potential became zero at a concentration of 280 mM (or 308 or 1500 mM for Rb or Cs, respectively) on extrapolation. PMID:4754874

Shipboard determination of radiocesium in seawater after the Fukushima accident: results from the 2011-2012 Russian expeditions to the Sea of Japan and western North Pacific Ocean.

PubMed

Ramzaev, V; Nikitin, A; Sevastyanov, A; Artemiev, G; Bruk, G; Ivanov, S

2014-09-01

A total of 88 seawater samples were collected during two Russian research expeditions (April-May 2011 and August-September 2012) to the Sea of Japan, the Oyashio Current region near Kuril Islands and the Kuroshio-Oyashio transition area in the western North Pacific Ocean. The observations were made aboard the R/V Pavel Gordienko and Akademik Shokalsky in order to study the impact of the Fukushima accident on radioactive contamination of the marine environment. On the board of a ship, the water samples were passed through filters to retain particles with the size of >1 micron. Cesium was extracted from the large volumes (100-3000 L) of the filtrated water using a selective fiber chemisorbent impregnated with copper ferrocyanide. Measurements of (134)Cs and (137)Cs activities in 83 samples of sorbents and 21 samples of filters were performed in the ship-based laboratory with a semiconductor HP-Ge detector. The quantified activity concentrations of dissolved radiocesium ranged from 1 Bq m(-3) to 34 Bq m(-3) for (137)Cs and from 0.2 Bq m(-3) to 29 Bq m(-3) for (134)Cs. Activity concentrations of (137)Cs and (134)Cs were strongly correlated with each other (r = 0.993, n = 59). The (137)Cs/(134)Cs activities ratio in the Fukushima-derived radiocesium inventory for the study areas was deduced to be 0.99 ± 0.03 (on 15 March 2011) and the pre-Fukushima background level of (137)Cs in seawater was estimated as 1.3 ± 0.3 Bq m(-3). The lowest activities of both isotopes were determined in the western part of the Sea of Japan near the Russian coast, while the maximal levels were observed in the open Pacific Ocean, some 500-800 km offshore the Fukushima Dai-ichi Nuclear Power Plant. Contamination with (134)Cs at a level of 0.3-2.6 Bq m(-3) was registered in seawater samples collected in 2011 near the Kuril Islands and Kamchatka in the Oyashio Current region. During the period from April-May 2011 to August-September 2012, activity concentrations of (137)Cs and (134)Cs in surface waters had decreased for all seven stations repeatedly sampled in the study. A detailed observation of radiocesium distribution within the water column down to the depth of 200 m at nine stations from the Kuroshio-Oyashio Interfrontal Zone and Kuroshio Extension in 2012 revealed maximal activity concentrations of both cesium radionuclides in the 100-200 m depth layer. The average inventory of Fukushima-derived (137)Cs in the top 200 m of the water column for the nine stations was estimated as 1.19 kBq m(-2) (decay corrected to 15 March 2011) which is 4.6 times higher than the background value of 0.26 kBq m(-2) expected for this depth. The monitoring results obtained in the study and relevant data published by others show that following the Fukushima accident, the Oyashio current acts as a provider of low-contaminated subarctic waters to the heavily contaminated Kuroshio-Oyashio mixed water region. Copyright © 2014 Elsevier Ltd. All rights reserved.

Relation between grain size and modal composition in deep-sea gravity-flow deposits. Example from the Voirons Flysch (Gurnigel nappe, Chablais Prealps, France)

NASA Astrophysics Data System (ADS)

Ragusa, Jérémy; Kindler, Pascal

2016-04-01

A coupled analysis of modal composition, grain size and sedimentary features of gravity-flow deposits in the Gurnigel nappe shows that the transition from coarse proximal to fine distal deposits is accompanied by a change in composition from siliciclastic to calcareous. Such compositional variation should be taken into account when interpretating deep-sea deposits if sampling is restricted to a single part of the fan. The Chablais Prealps (Haute-Savoie, France) represent a well-preserved accretionary wedge in the Western Alps. They comprise a stack of northward-thrusted sedimentary cover nappes originating from the Ultrahelvetic realm (distal part of the European margin) to the southern part of the Piemont Ocean. The present study focuses on the Voirons Flysch, belonging to the Gurnigel nappe, which includes four formations consisting of gravity-flow deposits (from bottom to top): (1) the Voirons Sandstone Fm., composed of channel to lobe deposits; (2) the Vouan Conglomerate Fm., represented by the proximal part of a channel system; (3) the Boëge Marls Fm., constituted by distal lobe deposits; finally, (4) the Bruant Sandstone Fm., which consists in channel to lobe deposits. Recent biostratigraphic results using planktonic foraminifers attributed a Middle to Late Eocene age to the Voirons Flysch, which was formerly believed to range from the Paleocene to the Middle Eocene (based on calcareous nannofossils). A total of 270 thin sections with stained feldspars were prepared, representing the four formations of the Voirons Flysch. Circa 300 extrabasinal grains were counted per thin section using the classic Indiana method. In addition, the quantity of intrabasinal grains (i.e. bioclasts, glauconite), cement and porosity was analysed. Cement was stained with alizarine and potassium ferrocyanide. 200 grain-size measurements on ca. 100 samples were performed using 3D conversion and statistical moment analysis. Sedimentary observations for each sampled bed were categorized following Mutti's turbiditic facies scheme. Cluster analysis on the composition of major grains discriminated 10 clusters which are merged into seven petrofacies (P1 - P7) following optical observations under the microscope: P1: poorly cemented porous arenite; P2: all porosity are filled by calcitic cement; P3: well-cemented volcano-clastic arenite; P4: red algae-rich highly cemented arenite to calcarenite; P5: highly cemented arenite; P6: globigerina-rich laminated calcarenite and P7: glauconitic quartzarenite. Grain-size distribution is grouped following the petrofacies. They provide a homogeneous distribution within each petrofacies with a gradual fining and progressively increasing sorting from P1 to P7. Moreover, Mutti's facies distribution indicates a progressive change towards more distal environments: from channel facies (F2 to F5) in P1-P3 to lobe facies (F8 to F9) in P4-P6. The washed composition of the P7 petrofacies is interpreted as distal turbidites that were reworked by bottom currents. The results presented here reveal a link between sand composition, grain size and gravity-flow facies. They highlight that composition of gravity flows is modified during their basinward transport. Consequently, coarse proximal deposits are more siliciclastic with limited filling of voids due to low carbonate contents. On the contrary, carbonate content increases significantly in the fine-grained calcarenites of the distal petrofacies. In distal settings, the segregation of light and porous foraminifera from the heavier siliciclastic fraction occurs under the increasing importance of traction currents.

Electron Paramagnetic Resonance: Elementary Theory and Practical Applications, Second Edition (John A. Weil and James R. Bolton)

NASA Astrophysics Data System (ADS)

Williams, Ffrancon

2009-01-01

The detection of electron magnetic resonance by Zavoiskii in the mid 1940s (1) ushered in a golden age of physical and chemical applications. Perhaps no single book did more to stimulate this development of EPR spectroscopy than the classic text by Wertz and Bolton (2) , which appeared in 1972. A revised version, with John A. Weil added as a co-author, was published by Wiley in 1994. This 2007 text is formally described as the second edition of the 1994 version. Wertz died shortly after the publication of the 1994 edition leaving Weil and Bolton as authors. In noting that the senior author (JAW) takes most of the responsibility for the content of this 2007 version, the Preface refers to it at one point as the "third edition", which of course is precisely how older readers will regard it. The main thrust of the book is decidedly on the physical aspects of EPR, so that it nicely complements the more chemical emphasis provided in the recent comprehensive text by Gerson and Hüber (3) . As the authors remark, the 2007 edition does not differ dramatically from the 1994 version. The titles of the 13 chapters remain the same except for chapter 11, which now refers to the "Noncontinuous" instead of the "Time-Dependent" Excitation of Spins. Recent developments are generally accommodated by a few extra pages in each chapter. Thus, chapter 1 on Basic Principles of Paramagnetic Resonance has been expanded from 31 to 36 pages to introduce the topics of parallel-field EPR, time-resolved EPR, "computerology", and EPR imaging. Chapter 2 on Magnetic Interactions is essentially unchanged while chapter 3 on Isotropic Hyperfine Effects has been expanded to include new sections on Deviations from the Simple Multinomial Scheme (3.7) and Some Interesting π-Type Free Radicals (3.9). Section 3.9 provides a useful corrective to the notion that the EPR method can detect and characterize almost any type of radical species. This welcome touch of realism is nicely illustrated by mentioning some of the difficulties regarding the use of EPR in studying the OH and hydrated electron (e aq - ) intermediates generated in liquid water by high energy radiation. The problems of detecting the OH radical due to its high reactivity and g-tensor anisotropy are well known and duly noted, but perhaps more striking is the fact that the EPR characterization of e aq - still remains uncertain even after more than 40 years of study. However, in suggesting the possibility that the uninformative singlet EPR spectrum assigned to e aq - could well be coming from the neutral hydronium (H 3 O) radical, the authors make the surprising assertion that the latter would be a π-type radical. In fact, H 3 O with its 9 valence electrons is a hypervalent radical and can be represented as an excess electron bound to a closed-shell H 3 O + structure, such that the unpaired electron occupies a Rydberg 3s-type orbital rather than a 2p-orbital on oxygen. This description is confirmed by high-level theoretical calculations (4, 5 ) which also indicate that H 3 O would only have marginal stability, its dissociation into a hydrogen atom and H 2 O being exothermic with an estimated barrier (0.004 eV) that is much less than kT at room temperature (0.026 eV). On the other hand, the e aq - species is relatively stable in purified water at pH 8 and quite long lived ( t 1/2 = 500 µs) with respect to its transformation to the hydrogen atom (6) . Moreover, e aq - has been shown to possess a unit negative charge (7) , so its assignment to H 3 O or even a solvated H 3 O (8 ) must be regarded as extremely questionable. Chapters 4 and 5 deal with the basic anisotropic Zeeman energy (g) and hyperfine (A) interactions that must be considered in the analysis of solid-state EPR spectra. Although these chapters are again much the same as in the earlier editions, Section 4.9, Comparative Overview, has been added and briefly discusses the pros and cons surrounding the methodology and information derived from studies of single crystal and powder spectra. In chapter 5, the important topic of anisotropic 1 H hyperfine coupling is again introduced via the V OH center in MgO but a much clearer example could have been used in this new edition. As it is, the illustrations in Fig. 5.1 are marred by the presence of additional lines in the spectra that are said to originate from other (related) defect centers. Although an effort has been made to mask these extra lines in the presented spectra, the general effect is inelegant and provides a needless distraction on a first reading of the subject. Chapters 6 through 8 contain only minor additions to the 1994 work. In chapter 6 on systems with S > 1/2, there are two brief new sections. Section 6.4 addresses the subject of Interacting Radical Pairs while Section 6.9 refers to the burgeoning literature on Modeling the Spin-Hamiltonian Parameters, with examples taken primarily from defect centers in crystalline quartz. Chapter 7 on Paramagnetic Species in the Gas Phase has likewise been expanded by Sections 7.8 on Reaction Kinetics and 7.9 on Astro-EPR, each consisting of a single paragraph. The diversity of radicals in outer space is illustrated by mentioning that in addition to the ubiquitous presence of H atoms that are readily detected by their well-known 1420.4 MHz signature emission, there exist exotic "coronium" ions in the solar corona. These are typified by Fe 13+ with an aluminum-like 3s 2 3p 1 electron configuration and a 2 P 1/2 ground state that should be detectable by EPR. In chapter 8 on Transition-Group Ions, Section 8.6 on A Ferroelectric System has been added; it describes in a few lines how the V 2+ ion can be used to probe the ferroelectric transition in potassium ferrocyanide trihydrate at 247 K. Chapter 9 on The Interpretation of EPR Parameters is essentially the same as that in the 1994 edition. An opportunity was clearly lost here to bring this material up to date. For example, in discussing the use of molecular-orbital (MO) theory for estimating the spin distribution in π-type organic radicals, reference is only made to the 1968 INDO program although it was supplanted in the 1990s by more accurate DFT (density functional theory) methods (9) . Moreover, in suggestions for further reading on the relations between hyperfine splittings and spin densities, the preponderance of the references are to works in the 1960s except for the 1993 Atherton book (10) and the 2003 text by Gerson and Hüber (3) . Appendix 9A on the use of Hückel MO calculations in π-electron systems is retained, but in Section 9.2 on π-type organic radicals there is no mention of the cases of symmetry-enhanced and symmetry-forbidden hyperconjugation in cyclic systems. Such effects are exemplified by the β-hydrogen couplings in the cyclohexadienyl and cyclobutenyl radicals where the symmetry of the SOMO is the determining factor and the usual McConnell-Heller equation (11) for the proportionality between the α-carbon spin density and -hydrogen hyperfine coupling does not apply ( 12, 13 ). In fact, these EPR results that depend on the amplitude of the wave function provide a direct illustration of the operation of the superposition principle in quantum mechanics ( 14 ). The above omissions bring to mind that at least one major area of EPR applications is not covered here in any depth. This pertains to work carried out over the last four decades in the field of physical organic chemistry. There are, for example, no references to the extensive studies of G. A. Russell, K. U. Ingold, and J. K. Kochi that have contributed greatly to our detailed understanding of both the structure and the kinetic transformations of organic radicals. Another field that is completely neglected is that of radical cations derived from saturated molecules, despite a considerable level of activity during the 1980s and 1990s as represented particularly by the innovative work of M. Iwasaki on alkanes and of L. B. Knight, Jr. on water, methane, and other small molecules. Even more surprisingly, given the book's emphasis on solid-state applications, there is hardly any mention of the considerable body of work on radiation damage to biological molecules such as DNA. Chapters 10 through 13 cover Relaxation Times, Noncontinuous Excitation, Double Resonance Techniques, and Other Topics, respectively. New sections include those on Longitudinal Detection (10.6), Dynamic Nuclear Polarization (10.9), Bio-Oxygen Measurements (10.10), and Spin Coherence and Correlation (11.8). As before, chapter 13 lists comprehensive sets of literature references on a wide variety of 17 EPR-related topics, new additions being the introductory three-line Apologia (13.1) and almost three pages on Geologic/Mineralogic Systems and Selected Gems (13.10), the latter perhaps reflecting the particular interests of the senior author in EPR studies of minerals. Nine appendices (A through I) round out the book and these cover a wide range of background reference material. Discussions of mathematical operations (A) and quantum mechanics (B) are followed by an exact solution of the energy eigenvalues as well as the derivation of selection rules for the transitions of the hydrogen atom and related species (C). Appendix D is new and deals with the physical properties and magnetic resonance aspects of photons. This is followed by discussions of instrumentation (E) and experimental considerations (F). Finally, there are listings of the main EPR-related books and chapters (G); fundamental constants, conversion factors, and tables of atomic hyperfine constants (H); and a comprehensive 11-page glossary of symbols (I). Altogether these appendices provide an invaluable summary of the theoretical foundations of EPR as well as a mine of readily accessible information and key data. On the back cover, the authors claim to have brought this popular text up to date and that it provides a basic understanding of the underlying theory, fundamentals, and applications of EPR. It is therefore useful to ask how well they have succeeded in this daunting task. The text has certainly been brought to a higher level of thoroughness and topicality through the addition of 96 extra pages relative to the 1994 edition. On the other hand, one can point to instances where newer material with clearer spectra would have been preferable to the continuation of the original version with its strong 1960s vintage identification. Also, although the authors take pains to emphasize that the text is not meant to be comprehensive, the omission of some recent areas of application where there have been striking advances is regrettable. Even with these imperfections, however, it still remains the text of choice for beginning students of EPR spectroscopy, and the demanding problem sets make the book eminently suitable for graduate courses specializing in solid-state physics and chemistry. It can also be highly recommended to researchers seeking applications that would harness the potential of EPR spectroscopy to related fields of study. The authors are to be congratulated on producing a truly formidable EPR bible that lays claim once again to being the standard work on the subject. Despite the ever-growing list of titles (15, 16), it is unlikely to be seriously challenged by competitors in the foreseeable future. Literature Cited Zavoiskii, E. J. Phys. U.S.S.R. 1945, 9, 211, 245; ibid. 1946, 10, 170. Wertz, J. E.; Bolton, J. R. Electron Spin Resonance: Elementary Theory and Practical Applications, McGraw-Hill ; New York, 1972. Gerson, F.; Hüber, W. Electron Spin Resonance Spectroscopy of Organic Radicals; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2003. Chen, F.; Davidson E. R. J. Phys. Chem. A 2001, 105, 10915-10921. Tachikawa, H.; Yamano T. Chem. Phys. Lett. 2001, 335, 305-310. Hart, E. J.; Gordon, S.; Fielden, E. M. J. Phys. Chem. 1966, 70, 150. Czapski, G.; Schwarz, H. A. J. Phys. Chem. 1962, 66, 471. Sobolewski, A. L.; Domcke, W. Phys. Chem. Chem. Phys. 2002, 4, 4-10. (a) Batra, R.; Giese, B.; Spichty, M.; Gescheidt, G.; Houk, K. N. J. Phys. Chem. 1996, 100, 18371-18379. (b) Adamo, C.; Barone, V.; Fortunelli, A. J. Phys. Chem. 1994, 98, 8648. (c) Barone, V. Theor. Chim. Acta 1995, 91, 113. (d) Barone, V. J. Phys. Chem. 1995, 99, 11659. (e) Hermosilla, L.; Calle, P.; Garcia de la Vega, J. M.; Sieiro, C. J. Phys. Chem. A 2005, 109, 1114; J. Phys. Chem. A 2005, 109, 7626. Atherton, N. M. Principles of Electron Spin Resonance; Prentice-Hall: New York, 1993. Heller, C.; McConnell, H. M. J. Chem. Phys. 1960, 32, 1535. Whiffen, D. H. Mol. Phys. 1963, 6, 223. Davies, A. G. J. Chem. Soc., Perkin Trans. 2 1999, 2461. Atkins, P. W. Quanta: A Handbook of Concepts; Clarendon Press: Oxford, 1974; p 231. Brustolon, M. R. Principles and Applications of Electron Paramagnetic Resonance Spectroscopy; Blackwell Publishers: Oxford, 2008. Lund, A.; Shiotani, M. Principles and Applications of Electron Spin Resonance; Springer-Netherland: Dordrecht, 2009.