Fluorescence of Metal–Ligand Complexes of Mono- and Di-Substituted Naphthalene Derivatives

In this work, metal ion complexes for several naphthalene derivatives have been investigated. Different working pH values were chosen: 2.5 for complexes with Zr(IV), 4.0 for complexes with Fe(III), 5.0 for complexes with Al(III), and 7.5 for complexes with Cu(II). A stoichiometry of 1:1 for all complexes except two has been established by use of the Benesi–Hildebrand method and the stability constants have been calculated. All complexes between naphthalene derivatives and Cu(II) and Fe(III) show fluorescence quenching. In the case of Al(III), all complexes provided enhanced fluorescence. For Zr(IV), only the complex with 3-hydroxy-2-naphthoic acid provided enhanced fluorescence. The value of the stability constants as a function of the substituents of naphthalene derivatives has been analyzed. One can conclude that Cu(II) showed the largest binding affinity for the mono-substituted derivatives. However, Al(III) and Zr(IV) produced greater selectivity for the di-substituted derivatives. Iron(III) showed no specific binding with any of the naphthalene derivatives.     

Nitrate reduction in clayey till by Fe(II) in clay minerals

In an area dominated by clayey till the distribution of nitrate and the Fe(II)/Fe(III) ratio have been measured below arable land till a depth of 20 metres. In the subsoil the nitrate (NO⁻ ₃) occurs in measurable quantities in the upper oxidised zone (until c. 3 m) and the Fe(II)/Fe(III) ratio is low. At the transition to the reduced zone the nitrate content decreases to below the detection limit and the Fe(II)/Fe(III) ratio is considerably increased. The results indicate that the Fe(II) in the clay minerals is oxidised by the nitrate which thereby is reduced.     

pH effect on the physicochemical characteristics and efficiency of electroflotation extraction of low-soluble iron subgroup metal compounds from aqueous solutions

This paper reports on our study of the pH effect of solutions on the average hydrodynamic diameter (d_av) of the particles of the disperse phase and the electrokinetic potential (ζ) of the particles of low-soluble iron subgroup metals compounds using Fe(II, III), Ni(II), and Co(II) compounds as an example. The pH effect of solutions on the efficiency of the electroflotation extraction of metal ions from aqueous solutions containing these ions in individual form or in mixture was studied. The efficiency of the electroflotation extraction of the low-soluble compounds of iron subgroup metals is directly related to the particle size and electrokinetic potential of the particles, which depend on рН. The maximum degree of particle extraction α reached 97–99% at рН values characterized by the maximum hydrodynamic diameter of particles (over 20 μm for Fe(II) and Co(II) compounds and over 50 μm for Fe(III) and Ni(II) compounds) at ζ potentials of up to–10 mV for systems approximated to real wastewater. In the case of the extraction of the disperse phase of the Fe(III)–Ni(II)–Co(II) multicomponent system, the synergic effect was observed: the coextraction of metals was more complete and effective, which may be due to suppressed negative charge. In the range of рН 10–11, the degree of extraction of the Fe(III) disperse phase did not exceed 74%; in the ternary system, it reached 94%.     

EPR and optical absorption characteristics of sodic plagioclase from granite pegmatite in Kadavur,India

The electron paramagnetic resonance (EPR) spectra of sodic plagioclase from dykes of granitic pegmatite occurring in the Kadavur area, Tamil Nadu, India, were examined at room temperature to identify paramagnetic impurities in a “low plagioclase” using EPR and optical techniques. The EPR spectra showed the presence of Fe(III) and Mn(II) impurities. After heating the plagioclase samples for various durations at 600 °C, it has been observed that the concentration of Mn(II) remained as such in one sample but completely disappeared in another sample, while there was no change in Fe(III) ion concentration after the heat treatment in either sample. Optical absorption spectra also showed Fe(II) and Fe(III) in addition to Ti(III) impurities in sodic plagioclase before heating, while after heating the relative concentration of Fe(II) and Fe(III) changed, accompanied by the disappearance of Ti(III).     

Composition and dynamics of iron in iron-poor ferritin

Mossbauer spectroscopy has been used to study Fe(III)-apoferritin complexes, formed after the addition of Fe(II) to apoferritin in air. The spectra showed the presence of divalent, dimeric trivalent and small clusters of trivalent iron. The amount of divalent and dimeric iron and the average iron-iron distance in the small clusters, diminished with time. The dynamic behaviour of iron in iron poor ferritin crystals, indicating that the iron is bound differently in the two systems and showing the role of different kinds of water in ferritin on protein dynamics.     

Tunable-frequency high-field electron paramagnetic resonance

A tunable-frequency methodology based on backward wave oscillator sources in high-frequency and -field EPR (HFEPR) is described. This methodology is illustrated by an application to three non-Kramers transition metal ion complexes and one Kramers ion complex. The complexes are of: Ni(II) (S=1) as found in dichlorobistriphenylphosphanenickel(II), Mn(III) (S=2) as found in mesotetrasulfonatoporphyrinatomanganese(III) chloride, Fe(II) (S=2) as found in ferrous sulfate tetrahydrate, and Co(II) (S=3/2) as found in azido(tris(3-tert-butylpyrazol-1-yl)hydroborate)cobalt(II). The above Ni(II) and Mn(III) complexes have been studied before by HFEPR using the multifrequency methodology based on Gunn oscillator sources, but not by the present method, while the Fe(II) and Co(II) complexes presented here have not been studied by any form of HFEPR. Highly accurate spin Hamiltonian parameters can be obtained by the experimental methodology described here, in combination with automated fitting procedures. This method is particularly successful in determining g-matrix parameters, which are very difficult to extract for high-spin systems from single frequency (or a very limited set of multi-frequency) HFEPR spectra, but is also able to deliver equally accurate values of the zero-field splitting tensor. The experimental methods involve either conventional magnetic field modulation or an optical modulation of the sub-THz wave beam. The relative merits of these and other experimental methods are discussed.     

Ultrasound-assisted biodiesel production by a novel composite of Fe(III)-based MOF and phosphotangestic acid as efficient and reusable catalyst

In this work, esterification of oleic acid by various alcohols is achieved with high yields under ultrasonic irradiation. This reaction performed with a novel heterogeneous catalyst that fabricated by heteropoly acid and Fe(III)-based MOF, namely MIL-53 (Fe). Syntheses of MIL-53 and encapsulation process carry out by ultrasound irradiation at ambient temperature and atmospheric pressure. The prepared composite was characterized by various techniques such as XRD, FT-IR, SEM, BET and ICP that demonstrate excellent catalytic activities, while being highly convenient to synthesize. The obtained results revealed that ultrasound irradiation could be used for the appropriate and rapid biodiesel production.     

Influence of Fe(III) on the Fluorescence of Lysozyme: a Facile and Direct Method for Sensitive and Selective Sensing of Fe(III)

Lysozyme is widely used for the synthesis of nanomaterials (e.g., gold nanoparticle) to fluorescently sense metal ions. However, the effect of metal ions on the fluorescence of lysozyme is not studied yet. Herein, we have explored the interactions of lysozyme with different metal ions to develop a direct sensing platform for Fe(III). It has been observed that the fluorescence of lysozyme was slightly decreased in the presence of Cu(II), Hg(II), As(V), Co(II), Cd(II), Cr(II), Fe(II), Mn(II), Pb(II), and Zn(II), while a significant decrease in the lysozyme fluorescence was observed for Fe(III). The effect of thermal stability on the fluorescence quenching was also studied from 25 to 60 °C. In the present study, the lysozyme sensing probe was able to selectively and accurately detect 0.5–50 ppm of Fe(III) with a LOD of 0.1 ppm (1.8 µM) at 25 °C.

     

非分离状态下FI-KR-FAAS测定铁的价态

建立了流动注射(FI)编结反应器(KR)在线预富集与火焰原子吸收光谱(FAAS)联用非分离状态下测定铁的价态的新方法。进样流速6.0 mL.min-1;进样时间60s,测定0.04 mg.L-1的Fe(Ⅲ)和Fe(Ⅱ),Fe(Ⅲ)和Fe(Ⅱ)的浓集系数(EF)分别为41和9;检出限分别为2.5和14.3μg.L-1;相对标准偏差(RSD,n=11)分别为2.3%和3.1%。以0.1‰φ的三乙醇胺为掩蔽剂,Fe(Ⅲ)和Fe(Ⅱ)在水样中的回收率分别为97%～101%和96%～100%。     

Spectroscopic Properties of Co-Fe Hydrotalcites

The spectroscopic properties of hydrotalcite-like compounds, containing Co(II) and Fe(III) in the layers, have been studied. In these materials, depending on the experimental conditions during synthesis, Co(II) becomes partially oxidized to Co(III). Although the environment of the cations is close to octahedral in all cases, Mossbauer data indicate a more symmetric environment for Fe(III) ions in samples not submitted to hydrothermal treatment. The FT-IR spectra show some distortion of the carbonate anions in the interlayer space.     

Characterization of ancient and modern papers by CW-EPR spectroscopy

Several old (15th to 18th century), new (1900–1950) and recently produced (after 1990) papers have been investigated by X-band continuous-wave electron paramagnetic resonance (EPR) spectroscopy. Signals from Cu(II), Fe(III), Mn(II) and radicals are apparent. A clear-cut distinction is observed between recently produced papers and the other samples: recent papers show just EPR signals from Mn(II) and sometimes small signals from Fe(III) in rhombic site, while the older samples show usually strong signals from Fe(III), Mn(II), Cu(II) and radicals. Furthermore, Mn(II) EPR signals from recent papers are characterized by small zero-field splitting (ZFS) parameters, indicating Mn(II) in high-symmetry sites, while older samples show broader Mn(II) EPR signals, typical for Mn(II) in low-symmetry sites (increased ZFS parameters).     

Kinetics and mechanisms of the sonolytic destruction of non-volatile organic compounds: investigation of the sonochemical reaction zone using several OH* monitoring techniques

This study investigates the sonolytic degradation mechanism of non-volatile organic compounds and reaction sites for its degradation using various tools that allow OH* to be monitored, such as: the spin-trapping method of OH* detection using non-volatile nitrone trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the hydrogen peroxide analytical methods and the p-chlorobenzoic acid (pCBA)-probe method. These methods can successfully monitor OH* produced during sonochemical processes, and identify the major reaction sites involving OH* of the three proposed reaction zones--within the cavity, in the bulk solution, and at the gas-liquid interfacial (shell) region. The patterns of hydrogen peroxide accumulation under the various conditions suggest that peroxides pre-form at the interfacial region, but the self-scavenging reaction by hydrogen peroxide simultaneously takes place in the same region. The simultaneously measured peroxide concentration, in the absence and presence of DMPO, and that of the DMPO-OH adduct indicated the peroxide production and DMPO-OH adduct formation reaction occur at the shell region. The sonolytic destruction efficiency of ultrasound coupled with Fe(II) has been also investigated. The coupled Fe(II)/ultrasound process was found to enhance the OH* production rate by 70% compared to the ultrasound process alone due to the reaction of Fe(II) with sonochemically produced hydrogen peroxide (Fenton's reaction). This accelerated reaction was also found to occur at the shell region rather than in the bulk solution. The enhancement effect of Fe(II)/ultrasound was also examined using pCBA as a probe. 2.8-fold and 3.6-fold increases of the pCBA degradation rate were observed at Fe(II) concentrations of 10 and 20 microM, respectively.     

Electric quadrupole interaction of 100Rh in antimony, hafnium and rhenium

The effects of the Mg(II)/Fe(III) ratio on the structure and Fe microenvironments in MgFe LDH substances were investigated. The LDHs were prepared by the co-precipitation method with Mg(II)/Fe(III) ratios from 2:1 to 6:1. The materials were characterized by ⁵⁷Fe Mössbauer spectroscopy and powder X-ray diffractometry. The ⁵⁷Fe Mössbauer spectra exhibited asymmetric doublet corresponding to high-spin Fe(III) microenvironments in all LDH structure. It was found that the quadrupole splitting decreased with increasing Mg(II)/Fe(III)ratio reflecting change in the electric field gradient due to the incorporation of different amounts of iron into the Mg-containing layers.     

Application of 57Fe-enriched synthetic ferrihydrite to speciate the product of bacterial reduction

We have sampled a clay lens with evidence of sulfide reduction from a texturally stratified sandy aquifer at Rømø, Denmark. A minor amount of synthetic, pure ⁵⁷Fe ferrihydrite was added to this sample and allowed to react for up to three months. The initial sample, the ⁵⁷Fe ferrihydrite, and samples taken from the reaction mixture were investigated by Mössbauer spectroscopy at temperatures between 15 and 298 K as sampled and following exposure to oxygen. The initial sample only contained Fe(II) (33% of the iron) and Fe(III) in silicates. The Fe(III) in the ferrihydrite is reduced to Fe(II) as evidenced by an increase of this component by bacterial activity. The Fe(II) component remains paramagnetic at temperatures down to 15 K. Similarly to naturally reduced sediments the new-formed Fe(II) is extremely reactive towards molecular oxygen. Following oxidation the reformed Fe(III) is found as ferrihydrite. The bonding of the Fe(II) is by electrostatical bonding (adsorbed) to the layer silicates as evidenced by a temperature scanning of the sample between 80 and 270 K.     

57Fe Mössbauer study of a deposit in an industrial cooling circuit supplied with raw river water

In this work, the nature of the deposit found inside an industrial cooling circuit (which consists of a mixture of different iron containing phases) has been characterized in detail by ⁵⁷Fe Mössbauer spectroscopy. Electron Paramagnetic Resonance spectroscopy was also used to check for the presence of other metals, mainly manganese and copper, detected by the Inductive Coupled Plasma method. We conclude that the deposit contains a large amount of Fe(III), probably consisiting of ferrihydrite nanoparticles and of goethite, either bulk or as large particles. It also contains traces of an Fe(II) species (about 3%), probably adsorbed on the iron oxides. Mn(II) and traces of Cu(II) are also present.     

Stereochemistry of New Nitrogen Containing Heterocyclic Aldehydes. II. Novel Bis-Bidentate Azodye Compounds

A novel family of chelating bis-bidentate azodye compounds¹ with Cu(II), Co(II), Ni(II), Fe(II), Hg(II), Pd(II), UO₂(II), Fe(III), Cr(III), La(III), Ru(III) and Zr(IV) has been prepared and characterized on the basis of analytical, magnetic, ¹H and ¹³C NMR, EPR and electronic spectral studies. Tentative structures for the polymeric complexes are proposed. The important IR bands and the main ¹H and ¹³C signals are assigned and discussed relative to the molecular structure. Various EPR parameters for Cμ(II), have been calculated. The ligand acts as a dibasic bis-bidentate chelating agent coordinating through CO, N=N, COOH and OH groups by replacement of a proton from the two latter groups. Considerable interest has also been focused on the synthesis of the azo compound and its polymeric metal complex due to its wide potential applications. The thermal decomposition behavior of the complexes is also discussed.     

光度法研究聚乙二醇-硫酸铵-邻苯三酚红体系中铋(Ⅲ), 铁(Ⅲ), 铜(Ⅱ), 镍(Ⅱ), 钴(Ⅱ), 铅(Ⅱ)的萃取分离

本文研究了在聚乙二醇(PEG)-硫酸铵[(NH_4)_2SO_4]-邻苯三酚红(PR)体系中Bi(Ⅲ),Fe(Ⅲ),Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Pb(Ⅱ)的萃取行为。实验结果表明,Bi(Ⅲ)在pH3.5～6.5及Fe(Ⅲ)在pH4.0～7.0范围内可以被PEG相几乎完全萃取,而Cu(Ⅱ),Co(Ⅱ)在pH1.0～7.0,Pb(Ⅱ)在pH2.0～7.0,Ni(Ⅱ)在pH1.0～4.5则不被萃取。从而实现了将Bi(Ⅲ)(pH3.5),Fe(Ⅲ)(pH5.0)与Cu(Ⅱ),Co(Ⅱ),Pb(Ⅱ),Ni(Ⅱ)混合离子的定量分离。同时探讨了PEG相的萃取机理。     

Mössbauer spectroscopic study of meteorites recovered on Antarctica

The chemical states of iron in sixteen Antarctic meteorites belonging to H-group chondrites were studied by means of Mössbauer spectroscopy. An Fe-Ni alloy, troilite, paramagnetic Fe(III), and two kinds of paramagnetic Fe(II) were observed in each meteorite. The Mössbauer parameters indicated that the Fe(II) components can be assigned to olivine and some pyroxenes. The relative area intensities of Fe(III) in the chondrites correlated positively with iodine content, which was determined by radiochemical neutron activation analysis, and those of two Fe(II)-species correlated negatively with the content. On the basis of the data on the halogen and the Mössbauer spectrocopy, the terrestrial contamination on Antarctic meteorites is discussed.     

Studies of iron in deep-sea sediments by Mössbauer spectroscopy

The distribution of the forms of Fe in the solid phases in core samples of sediments from the Peru Basin has been investigated by Mössbauer spectroscopy with special attention to the cause of the sharp color transition between an upper green colored and a lower tan colored part. An important part of sample handling includes strict exclusion of oxygen during preparation of absorbers and measurements at cryogenic temperatures. The measurement strategy includes measurements between 77 K and 300 mK in zero external magnetic field, supplemented by measurements in external magnetic fields at 4.2 and 300 mK (up to 6.2 and 1 T, respectively). The temperature scans allow detection, identification and quantification of superparamagnetic iron oxides (goethite and hematite). The oxides are only present in samples from the upper tan-colored part of the core. The major part of the Fe(II) and Fe(III) (>80%) is present in a magnetic structure similar to that of layer silicates. The relative Fe(II) content of the layer silicates is practically identical to that determined from the paramagnetic components measured at liquid nitrogen temperature. This shows that the color transition in the sediment coincides with a change in the relative Fe(II) content in layer silicates from 11 to 37%. The color change can thus be explained by an increase in occurrence of Fe(II)–Fe(III) pairs exhibiting absorption bands due to intervalence electron transfer.     

Degradation of Acid Blue 25 in aqueous media using 1700 kHz ultrasonic irradiation: ultrasound/Fe(II) and ultrasound/H2O2 combinations

In this work, the sonolytic degradation of an anthraquinonic dye, C.I. Acid Blue 25 (AB25), in aqueous phase using high frequency ultrasound waves (1700 kHz) for an acoustic power of 14 W was investigated. The sonochemical efficiency of the reactor was evaluated by potassium iodide dosimeter, Fricke reaction and hydrogen peroxide production yield. The three investigated methods clearly show the production of oxidizing species during sonication and well reflect the sonochemical effects of high frequency ultrasonic irradiation. The effect of operational conditions such as the initial AB25 concentration, solution temperature and pH on the degradation of AB25 was studied. Additionally, the influence of addition of salts on the degradation of dye was examined. The rate of AB25 degradation was dependent on initial dye concentration, pH and temperature. Addition of salts increased the degradation of dye. Experiments conducted using distilled and natural waters demonstrated that the degradation was more efficient in the natural water compared to distilled water. To increase the efficiency of AB25 degradation, experiments combining ultrasound with Fe(II) or H₂O₂ were conducted. Fe(II) induced the dissociation of ultrasonically produced hydrogen peroxide, leading to additional OH radicals which enhance the degradation of dye. The combination of ultrasound with hydrogen peroxide looks to be a promising option to increase the generation of free radicals. The concentration of hydrogen peroxide plays a crucial role in deciding the extent of enhancement obtained for the combined process. The results of the present work indicate that ultrasound/H₂O₂ and ultrasound/Fe(II) processes are efficient for the degradation of AB25 in aqueous solutions by high frequency ultrasonic irradiation.