• Journal of Photoscience
• /
• v.6 no.3
• /
• pp.129-133
• /
• 1999

Microperoxidase 8 (MP8) has been prepared by sequential hydrolysis of cytochrome C by pepsin and trypsin. This five-coordinated heme-octapetide fragment provides a uniques structure to evaluate the electronic coupling efficiency to the iron through axial position and porphyrin edge. At alkali pH, Ru(bpy)2(im)22+ is completely quenched in AcMP8Ru complex . Transient kinetics measurement showed the decay rate to be ~1 $\times$1012S-1. Ruthenium bipyridine complex with a carboxyl group substituted bipyridine has been prepared adn reacted with MR 8 to yield N-terminus bound RuMP8 complex. The luminescence decay rate has been measured as 1 $\times$109S-1. By using semiclassical electron transfer theory, we found the electron transfer efficiency through axial positioin of iron prophyrin is as good through prophyrin edge.

• Environmental Engineering Research
• /
• v.25 no.2
• /
• pp.197-204
• /
• 2020

A number of different nanoscale zero-valent iron (nZVI) materials have been prepared and compared depending on the desired properties for the particular application, but different physicochemical properties of this prepared nZVI make it difficult to universally compare and standardize them to the same scale. In this study, we aimed to demonstrate a simple microplate-based colorimetric assay using 4-chlorophenol as an indicator with respect to the remediation of real treatment targets, such as trichloroethylene (TCE), 1,1,1-trichloroethane (TCA), and atrazine. Effect of nickel contents on 4-chlorophenol reduction was successfully investigated by the miniaturized colorimetric assay. In the same manner, the effect of nickel contents on dehalogenation of TCE, TCA, and atrazine was investigated and the pseudo-first-order kinetic constants were compared with the results for 4-chlorophenol. The similar pattern could be observed between 4-chlorophenol reduction obtained by colorimetric assay and TCE, TCA, atrazine reduction obtained by a traditional chromatographic method. The reaction kinetics does not match perfectly, but the degree of reaction can be estimated. Therefore, the colorimetric assay can be a useful and simple screening tool to determine nZVI reactivity toward halogenated organics before it is applied to a particular remediation site.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.8
• /
• pp.2358-2366
• /
• 2013

Iron oxide (ferrihydrite, hematite, and magnetite) coated silica gels were prepared using a low-cost, easily-scalable and straightforward method as the adsorbent material for arsenic removal application. Adsorption of the anionic form of arsenic oxyacids, arsenite ($AsO^{2-}$) and arsenate ($AsO{_4}^{3-}$), onto hematite coated silica gel was fitted against non-linear 3-parameter-model Sips isotherm and 2-parameter-model Langmuir and Freundlich isotherm. Adsorption kinetics of arsenic could be well described by pseudo-second-order kinetic model and value of adsorption energy derived from non-linear Dubinin-Radushkevich isotherm suggests chemical adsorption. Although arsenic adsorption process was not affected by the presence of sulfate, chloride, and nitrate anions, as expected, bicarbonate and silicate gave moderate negative effects while the presence of phosphate anions significantly inhibited adsorption process of both arsenite and arsenate. When the actual efficiency to remove arsenic was tested against 1 L of artificial arsenic-contaminated groundwater (0.6 mg/L) in the presence competing anions, the reasonable amount (20 g) of hematite coated silica gel could reduce arsenic concentration to below the WHO permissible safety limit of drinking water of $10{\mu}g/L$ without adjusting pH and temperature, which would be highly advantageous for practical field application.

• KSBB Journal
• /
• v.26 no.2
• /
• pp.119-125
• /
• 2011

In the synthesis of nanoparticles, much attention has been paid to regulating the particle size. There has been a possible evident that using the central cavity (core) of the protein ferritin has a greatly significant influence on it because the core can generate the nanometer-sized mineral particles of variable metal ions. In this report, recombinant human L-ferritins produced from Saccharomyces cerevisiae were purified and their molecular properties were characterized. The cDNA for human ferritin L chain was also expressed in another host such as Escherichia coli, and the properties of recombinant L-ferritins were compared. From isoelectric focusing experiment, the L-ferritin from the recombinant yeast showed no indication of N-glycosylation. Some post-translational modifications other than N-glycosylation were speculated in the L-ferritins from yeast. A difference was made in the L-ferritins in their iron uptake rates and the initial rate of the L-ferritin from yeast was slightly increased. The reconstitution yield and size distribution of the core minerals were analyzed in the L-ferritins by transmission electron microscopy. The L-ferritin from yeast with higher reconstitution yield (54.5%) showed slightly larger sizes (mean 6.92 nm) with narrower size distribution than the L-ferritin from E. coli. It is, in conclusion, speculated that L-ferritin from yeast is relatively superior to the other, in view of the size of nanoparticle and its relative homogeneity.

• Journal of Korea Soil Environment Society
• /
• v.4 no.1
• /
• pp.97-108
• /
• 1999

Reduction 2, 4, 6-trinitrotoluene by zero valent iron was studied in a batch reactor under anoxic conditions. Results showed that the removal of trinitrotoluene (TNT)followed a pseudo-first order reaction and the rate was linearly dependent on the available reactive surfau area of the zero valent iron surface area, resulting a rate constant of 0.0981min$^{1}m$$^{-2}m$. High concentrations of the final product, presumably triaminotoluene which needs to be treated by other means, accumulated in the solution. However , little amount of TAT was extracted from the metal surface by using acetonitrile or phosphate buffered water (pH 7.0). Other common major intermediate in biological TNT degradation, a group of aminodinitrotoluenes, was not detected in the solution. Therefore, it is postulated that the reduction of nitro group by $Fe^0$ occurs simultaneously in all three positions and a TNT reduction model by zero valent iron was suggested.

• Journal of Microbiology and Biotechnology
• /
• v.20 no.3
• /
• pp.532-541
• /
• 2010

Peroxidase-like activity of Vitreoscilla hemoglobin (VHb) has been recently disclosed. To maximize such activity, two catalytically conserved residues (histidine and arginine) found in the distal pocket of peroxidases have successfully been introduced into that of the VHb. A 15-fold increase in catalytic constant ($k_{cat}$) was obtained in P54R variant,which was presumably attributable to the lower rigidity and higher hydrophilicity of the distal cavity arising from substitution of proline to arginine. None of the modifications altered the affinity towards either $H_2O_2$ or ABTS substrate. Spectroscopic studies revealed that VHb variants harboring the T29H mutation apparently demonstrated a spectral shift in both ferric and ferrous forms (406-408 to 411 nm, and 432 to 424-425 nm, respectively). All VHb proteins in the ferrous state had a $\lambda_{soret}$ peak at ~419 nm following the carbon monoxide (CO) binding. Expression of the P54R mutant mediated the downregulation of iron superoxide dismutase (FeSOD) as identified by two-dimensional gel electrophoresis (2-DE) and peptide mass fingerprinting (PMF). According to the high peroxidase activity of P54R, it could effectively eliminate autoxidation-derived $H_2O_2$, which is a cause of heme degradation and iron release. This decreased the iron availability and consequently reduced the formation of the $Fe^{2+}$-ferric uptake regulator protein ($Fe^{2+}$-Fur), an inducer of FeSOD expression.

• Journal of Soil and Groundwater Environment
• /
• v.11 no.6
• /
• pp.83-91
• /
• 2006

Reduction kinetics and the behaviour of intermediate of three high explosives (HMX, RDX, and TNT) were studies in batch reactors using nano- or micro- size zero valent iron(nZVI or mZVI) as reducing agent. The kinetic constants normalized by the mass of iron ($k_M$) or by the surface area ($k_{SA}$) were measured and compared along with the changes in the concentrations of intermediates. Results showed that $k_M$ and $k_{SA}$ values were not suitable to fully explain the behaviour of mother compounds and reduced intermediates in the batch reactor. The concentrations of initial explosives degradation products, such as nitroso-RDXs, nitroso-HMXs, and hydroxylamino-TNTs, were higher in mZVI treated reactor than in nZVI treated reactor, whereas more reduced polar intermediates such as TAT were accumulated in the nZVI reactor. Therefore, a new parameter, which accounted for the intermediates reduction, needs to be developed.

• Resources Recycling
• /
• v.25 no.3
• /
• pp.74-81
• /
• 2016

Study on chlorination of ilmenite ore were carried out by using PVC(polyvinyl chloride) as the chlorinating agent in a static bed reactor for selective removal of iron. The effect of amount of PVC and reaction temperature were investigated. It was found that the removal ratio of iron increased with amount of PVC and temperature. After reaction with HCl gas generated from PVC, porous surface of the specimens were observed. As a result, HCl gas could react with iron in the central portion of ilmenite particle through these pores. Examination of data using kinetic model suggest that the selective chlorination rate is controlled by chemical reaction at the interface of particles. The activation energy for the selective chlorination of ilmenite using PVC was calculated as 20.47 kJ/mol.

• Journal of Soil and Groundwater Environment
• /
• v.25 no.1
• /
• pp.62-73
• /
• 2020

PAHs commonly found in industrial sites such as manufactured gas plants (MGP) are potentially toxic, mutagenic and carcinogenic, and thus require immediate remediation. In-situ chemical oxidation (ISCO) is known as a highly efficient technology for soil and groundwater remediation. Among the several types of oxidants utilized in ISCO, persulfate has gained significant attention in recent years. Peroxydisulfate ion (S₂O₈^2-) is a strong oxidant with very high redox potential (E⁰ = 2.01 V). When mixed with Fe²⁺, it is capable of forming the sulfate radical (SO₄^-·) that has an even higher redox potential (E⁰ = 2.6 V). In this study, the influence of various iron activators on the persulfate oxidation of PAHs in contaminated soils was investigated. Several iron sources such as ferrous sulfate (FeSO₄), ferrous sulfide (FeS) and zero-valent iron (Fe(0)) were tested as a persulfate activator. Acenaphthene (ANE), dibenzofuran (DBF) and fluorene (FLE) were selected as model compounds because they were the dominant PAHs found in the field-contaminated soil collected from a MGP site. Oxidation kinetics of these PAHs in an artificially contaminated soil and the PAH-contaminated field soil were investigated. For all soils, Fe(0) was the most effective iron activator. The maximum PAHs removal rate in Fe(0)-mediated reactions was 92.7% for ANE, 83.0% for FLE, and 59.3% for DBF in the artificially contaminated soil, while the removal rate of total PAHs was 72.7% in the field-contaminated soil. To promote the iron activator effect, the effects of hydroxylamine as a reducing agent on reduction of Fe³⁺ to Fe²⁺, and EDTA and pyrophosphate as chelating agents on iron stabilization in persulfate oxidation were also investigated. As hydroxylamine and chelating agents (EDTA, pyrophosphate) dosage increased, the individual PAH removal rate in the artificially contaminated soil and the total PAHs removal rate in the field-contaminated soil increased.

• Clean Technology
• /
• v.15 no.3
• /
• pp.194-201
• /
• 2009

Reductive reactivity of zero-valent iron nanoparticles was investigated for removal of nitrate-nitrogen which is considered one of the major water pollutants. To elucidate the difference in reactivity between preparation methods, iron nanoparticles were synthesized respectively from microemulsion and aqueous solution of ferric ions. Iron nanoparticles prepared from microemulsion were deposited on aluminum by electrophoretic method, and their reaction kinetics was compared to that of the same nanoparticles suspended in aqueous batch reaction. With an approximation of pseudo-first-order reaction, rate constants for suspended nanoparticles prepared from microemulsion and dilute aqueous solution were $3.49{\times}10^{-2}min^{-1}$ and $1.40{\times}10^{-2}min^{-1}$, respectively. Iron nanoparticles supported on aluminum showed ca. 30% less reaction rate in comparison with the identical nanoparticles in suspended state. However, supported nanoparticles showed the superior effectiveness in terms of nitrate-nitrogen removal per zero-valent iron input especially when excess amounts of nitrates were present. Iron nanoparticles deposited on aluminum maintained reductive reactivity for more than 3 hours, and produced nitrogen gas as a final reduction product of nitrate-nitrogen.