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At least 19 recordsLinked to original sources
PubMed1991

An investigation of Chromatium vinosum high-potential iron-sulfur protein by EPR and Mossbauer spectroscopy; evidence for a freezing-induced dimerization in NaCl solutions.

The high-potential iron-sulfur protein (HiPIP) from Chromatium vinosum contains a cubane prosthetic group that shuttles between the [4Fe-4S]3+,2+ states. We find that the EPR spectra from this protein can be explained as a sum of two components, a major one with g = 2.02; 2.04; 2.12, and a minor one with g = 2.04; 2.07; approximately 2.13. In the presence of 0.1-2.0 M NaCl, freezing induces polymerization of the protein (presumably dimers), which is detected as intercluster spin-spin interaction in the EPR. The observed spin-spin interactions are interpreted as being due to two very similar dimeric structures in an approx. 1:2 ratio. Computer simulation of the X- and Q-band EPR spectra shows that the z-components of the g-tensors in each dimer pair must be co-linear, with center-to-center distances between the clusters of approximately 13 A and approximately 16 A. Inspection of possible dimeric structures of C. vinosum HiPIP by standard molecular graphics procedures revealed that the Fe/S cluster is exposed toward a flattened surface and is accessible to solvent. Moreover, the Fe/S clusters in two HiPIP molecules can easily achieve a center-to-center distance of approximately 14 A when approaching along a common 3-fold axis that extends through the S4 sulfur atom of the cubane; the z-component of the EPR g-tensor is co-linear with this symmetry axis.

Chromatium↗
PubMed2006

Radiation exposure in mossbauer spectroscopy.

This paper deals with the risks involved in routine operations as well as in potentially hazardous management of radioactive sources in a typical Mössbauer spectroscopy research laboratory. It comes from a direct experience at the University of Parma, Italy, and from information obtained from more than 50 different Mössbauer laboratories all over the world. A review of the normal procedures performed by researchers and technicians in the Mössbauer laboratory is presented along with the relative dose evaluations. Radiation doses have been calculated and measured from various situations, ranging from daily operations and maintenance work to radiation risks in case of incorrect procedures and/or device failures.

Body Burden↗
PubMedDate not supplied

[Possible effects of the influence of dynamic disorder of biological systems on characteristics of intramolecular mobility, determined by Mossbauer spectroscopy].

A model for describing dynamic properties of proteins is proposed. The model involves the distribution over amplitudes and correlation times of intramolecular dynamics. It has been shown that distribution parameters and its temperature dependence have a great influence upon the values of experimental dynamic characteristics. Besides the discrepancy between the real and experimental temperature, dependence of characteristics on intramolecular dynamics can be observed.

Models, Chemical↗
PubMed1989

[Application of Mossbauer spectroscopy to the study of hemoglobinopathies. Preliminary experience].

37Fe Moessbauer spectroscopy has been applied to the study of iron deposits in patients with altered iron metabolism. Haematological parameters were also studied in order to analyse their relationship with Moessbauer results. Within the aim of this research, 12 samples of packed red blood cells were analysed: 6 with beta-thalassaemia major, 2 with S-beta-thalassaemia, 1 with sickle cell anaemia and 3 from normal subjects used as control for Moessbauer spectroscopy. Moessbauer spectra of 6 red blood cells samples showed that besides the two components, i.e., oxy and deoxy haemoglobin present in samples of normal subjects, appears a third component with Moessbauer parameters corresponding to ferritin-like iron. Correlation of % transferrin saturation (TS %) with ferritin-like iron (r = 0.90, p less than 0.05) as well as between TS % and the ratio ferritin-like iron/Hb iron (r = 0.91, p less than 0.05) was found. A tendency to correlation of serum ferritin (SF) with ferritin-like iron (r = 0.90, p less than 0.05) as well as between TS % and the ratio ferritin-like iron/Hb iron (r = 0.91, p less than 0.05) was found. A tendency to correlation of SF with ferritin-like iron (r = 0.78) and with the ratio ferritin-like iron/Hb iron, was also observed. It can be concluded that Moessbauer spectroscopy could be a useful technique in the study of this kind of pathology.

Adolescent↗
PubMed1994

[Mossbauer spectroscopy of iron in substantia nigra in Parkinson disease and controls].

Mössbauer spectroscopy was used to study iron content, its redox state and binding sites in substantia nigra from parkinsonian and control brains. Measurements performed on fresh frozen samples demonstrated the presence of ferric iron only, both in disease and control. We found no difference in the total amount of iron in substantia nigra between the disease and control. Mössbauer spectra observed at 4.1 K in fresh frozen samples were different from those obtained in formalin fixed samples. In the fresh frozen samples only ferritin like iron was observed, whereas in the formalin fixed samples also non-ferritin iron was detected. It seems that in formalin fixed brains, during years, iron is released from ferritin and bound to an iron chelator or formalin.

Aged↗
PubMed1990

Glutaraldehyde effect on hemoglobin: evidence for an ion environment modification based on electron paramagnetic resonance and Mossbauer spectroscopies.

Glutaraldehyde is a widely used reagent for hemoglobin cross-linking in blood substitutes research. However, hemoglobin polymerization by glutaraldehyde involves modifications of its functional properties, such as oxygen affinity, redox potentials, and autoxidation kinetics. The aim of this article is to investigate, by electron paramagnetic resonance and Mossbauer spectroscopies, the changes that occur in the iron environment after glutaraldehyde cross-linking. Spectrometric studies were performed with native hemoglobin and hemoglobin cross-linked as soluble and insoluble polymers. Spectrometry data comparison with glutaraldehyde-modified hemoglobin functional properties allows to interpret from a structural point of view that glutaraldehyde action occurs as a decrease of the O--N(F8His) distance, an increase of the Fe--N(F8His) bond length, and the decrease of the distal-side steric hindrance.

Cross-Linking Reagents↗
PubMedDate not supplied

[Mossbauer spectroscopy of cells of cyanobacteria Synechocystis sp. PCC 6803 devoid of photosystem I and containing inactive phycobilisomes].

Mossbauer spectra of the psaAB mutant of Synechocystis sp. PPC 6803 devoid of photosystem I grown in a 57Fe-containing medium were measured. The spectrum is a broadened doublet whose size (about 20%) and parameters (isomeric shift delta = 0.3 mm/s and quadrupole splitting delta = 0.8 mm/s) suggest the presence of abundant nanoclusters of Fe3+ oxides in a superparamagnetic state tightly bound to the membrane. Treatment of cells with EDTA was accompanied by a substantial (tenfold) decrease in the amount of iron nonspecifically bound to the membrane and the appearance of Fe2+ localized, probably, inside cells and/or cell membranes. In addition, the spectrum of washed cells exhibited superfine magnetic splitting due to iron oxide clusters greater in size than nanoclusters present in the membrane prior to EDTA treatment.

Bacterial Proteins↗
PubMed1993

Reflectance and Mossbauer spectroscopy of ferrihydrite-montmorillonite assemblages as Mars soil analog materials.

Spectroscopic analyses show that Fe(3+)-doped smectites prepared in the laboratory exhibit important similarities to the soils on Mars. Ferrihydrite has been identified as the interlayer ferric component in Fe(3+)-doped smectites by a low quadrupole splitting and magnetic field strength of approximately 48 tesla in Mossbauer spectra measured at 4.2 K, as well as a crystal field transition at 0.92 micrometer. Ferrihydrite in these smectites explains features in the visible-near infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. Clay silicates have met resistance in the past as Mars soil analogs because terrestrial clay silicates exhibit prominent hydrous spectral features at 1.4, 1.9, and 2.2 micrometers; and these are observed weakly, if at all, in reflectance spectra of Mars. However, several mechanisms can weaken or compress these features, including desiccation under low-humidity conditions. The hydration properties of the interlayer cations also effect band strengths, such that a ferrihydrite-bearing smectite in the Martian environment would exhibit a 1.9 micrometers H2O absorption that is even weaker than the 2.2 micrometers structural OH absorption. Mixing experiments demonstrate that infrared spectral features of clays can be significantly suppressed and that the reflectance can be significantly darkened by mixing with only a few percent of a strongly absorbing opaque material. Therefore, the absolute reflectance of a soil on Mars may be disproportionately sensitive to a minor component. For this reason, the shape and position of spectral features and the chemical composition of potential analogs are of utmost importance in assessing the composition of the soil on Mars. Given the remarkable similarity between visible-infrared reflectance spectra of soils in bright regions on Mars and Fe(3+)-doped montmorillonites, coupled with recent observations of smectites in SNC meteorites and a weak 2.2 micrometers absorption in some Mars soils, ferrihydrite-bearing smectites warrant serious consideration as a Mars soil analog.

Aluminum Silicates↗
PubMed1969

Mossbauer spectroscopy of the iron-sulfur proteins.

The Mössbauer spectra of (57)Fe in two plant ferredoxins (from spinach and Euglena) and in xanthine oxidase have been measured at a series of temperatures and magnetic fields, and are found to be similar in all three proteins. In the oxidized state the iron is nonmagnetic. In the reduced state, the iron nuclei show magnetic hyperfine interaction with an electron spin S of (1/2), producing an effective field of about 180 kG at the nuclei.

Euglena↗
PubMedDate not supplied

[Study of ferredoxins in membranes of Rhodopseudomonas spheroides by means of Mossbauer spectroscopy].

Mössbauer spectra were investigated in membranes (chromatophores) of Rhodopseudomonas sphaeroides, enriched in 57Fe, over a temperature range from 4.2 to 300 K. The spectrum of isolated chromatophores is a symmetric doublet characterized by an isomeric shift delta=0.60+/-0.03 mm/s, quadrupole splitting delta=0.54+/-0.03 mm/s and a width gamma delta of 1.42+/-0.04 mm/3 at half maximum. These parameters, which are in fact characteristic of the Mössbauer spectra of bacterial ferredoxins, appeared practically invariable over a wide range of temperatures. The spectrum of dithionite-treated chromatophores, measured immediately after dithionite treatment, exhibits, in addition, a doublet having parameters characteristic of high-spin bivalent iron. The doublet linewidth of the Fe2+ (S=2) iron is equal, at room temperature, to the emission spectrum linewidth. At 4K, some broadening of the spectrum is observed, which is of magnetic origin. The intensity of the Fe2+(S=2) doublet from a dithionite-treated sample shows a pronounced drop after several days of storage, with the intensity of the initial doublet rising. The overall area under the spectra, the linewidth and shape are not changed. Based on experimental data obtained, possible models of the active center composed of most frequently encountered membrane-bound ferredoxins of the photosynthetic bacterium Rhodopseudomonas sphaeroides are discussed.

Cell Membrane↗
PubMed1999

A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration.

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

Colorado↗
PubMed2004

The complex between hydrogenase-maturation proteins HypC and HypD is an intermediate in the supply of cyanide to the active site iron of [NiFe]-hydrogenases.

Carbamoylphosphate has been shown to be the educt for the synthesis of the CN ligands of the NiFe metal centre of hydrogenases from Escherichia coli. In the absence of carbamoylphosphate, cells accumulate a complex of two hydrogenase maturation proteins, namely HypC and HypD for the synthesis of hydrogenase 3. A procedure for the purification of wild-type HypD protein or of a biologically active derivative carrying the Strep-tagII((R)) at the N terminus has been developed. HypD is a monomeric protein possessing about 4 mol of iron per mol of protein. Electron paramagnetic resonance (EPR) and Mossbauer spectroscopy demonstrated that the iron is present as a diamagnetic [4Fe-4S](2+) cluster. The complex between HypC and HypD can be cross-linked by a number of thiol and primary amine-specific linkers. When HypD and HypC were overproduced side-by-side with HypE, the HypC-HypD complex contained substoichiometric amounts of HypE whose proportion in the complex could be augmented when HypF was also overproduced. HypE trapped in this complex could be carbamoylated by protein HypF and after dehydration transferred the cyano group to the HypC-HypD part of the complex. Free HypC and HypD were not cyanated by HypE-CN. An active HypC-HypD complex from anaerobic cells was inactivated by incubation with K(3)[Fe(CN)(6)] but not with K(4)[Fe(CN)(6)]. The results suggest the existence of a dynamic complex between the hydrogenase maturation proteins HypD, HypC, HypE and HypF, which is the site of ligand biosynthesis and attachment to the iron atom of the NiFe site in hydrogenase 3.

Catalytic Domain↗
PubMed1997

FNR is a direct oxygen sensor having a biphasic response curve.

FNR is a transcription regulator that controls the expression of target genes in response to anoxia. Anaerobiosis is accompanied by the acquisition of two [4Fe-4S]2+ clusters per FNR dimer and the ability to bind DNA site-specifically. Oxidation of the [4Fe-4S]2+ form of FNR by O2 produced a non-DNA-binding, transcriptionally inactive form which also contains an iron-sulfur cluster, recently identified by Mossbauer spectroscopy as a [2Fe-2S] cluster (Khoroshilova et al., 1997, PNAS. 94, 6078). Complete conversion needed at least 2.5-3.0 molecules of O2 per [4Fe-4S]2+ cluster. Using sub-stoicheiometric amounts of air-saturated buffer, stable equilibria were established in which the [4Fe-4S]2+ and [2Fe-2S]2+ forms co-exist and no EPR detectable free ferric ions were released. In contrast, a 20-fold molar excess K3Fe(CN)6 was required to oxidise the [4Fe-4S]2+ cluster and in this case, ferric ions were released. FNR is therefore a sensitive O2 sensor.

Anaerobiosis↗
PubMed1996

Structural fluctuations of myoglobin from normal-modes, Mössbauer, Raman, and absorption spectroscopy.

A normal-mode analysis of carbon monoxymyoglobin (MbCO) and deoxymyoglobin (Mb) with 170 water molecules is performed for (54)Fe and (57)Fe. A projection is defined that extracts iron out-of-plane vibrational modes and is used to calculate spectra that can be compared with those from resonance Raman scattering. The calculated spectra and the isotopic shift (57)Fe versus (54)Fe agree with the experimental data. At low temperatures the average mean square fluctuations (MSFs) of the protein backbone atoms agree with molecular dynamics simulation. Below 180 K the MSFs of the heme iron agree with the data from Mossbauer spectroscopy. The MSFs of the iron atom relative to the heme are an order of magnitude smaller than the total MSFs of the iron atom. They agree with the data from optical absorption spectroscopy. Thus the MSFs of the iron atom as measured by Mossbauer spectroscopy can be used to probe the overall motion of the heme within the protein matrix, whereas the Gaussian thermal line broadening of the Soret band and the resonance Raman bands can be used to detect local intramolecular iron-porphyrin motions.

Heme↗
PubMed2000

Synthesis of tin and tin oxide nanoparticles of low size dispersity for application in gas sensing.

Nanocomposite core-shell particles that consist of a Sn0 core surrounded by a thin layer of tin oxides have been prepared by thermolysis of [(Sn(NMe2)2)2] in anisole that contains small, controlled amounts of water. The particles were characterized by means of electronic microscopies (TEM, HRTEM, SEM), X-ray diffraction (XRD) studies, photoelectron spectroscopy (XPS), and Mossbauer spectroscopy. The TEM micrographs show spherical nanoparticles, the size and size distribution of which depends on the initial experimental conditions of temperature, time, water concentration, and tin precursor concentration. Nanoparticles of 19 nm median size and displaying a narrow size distribution have been obtained with excellent yield in the optimized conditions. HRTEM, XPS, XRD and Mossbauer studies indicate the composite nature of the particles that consist of a well-crystallized tin beta core of approximately equals 11 nm covered with a layer of approximately equals 4 nm of amorphous tin dioxide and which also contain quadratic tin monoxide crystallites. The thermal oxidation of this nanocomposite yields well-crystallized nanoparticles of SnO2* without coalescence or size change. XRD patterns show that the powder consists of a mixture of two phases: the tetragonal cassiterite phase, which is the most abundant, and an orthorhombic phase. In agreement with the small SnO2 particle size, the relative intensity of the adsorbed dioxygen peak observed on the XPS spectrum is remarkable, when compared with that observed in the case of larger SnO2 particles. This is consistent with electrical conductivity measurements, which demonstrate that this material is highly sensitive to the presence of a reducing gas such as carbon monoxide.

Journal Article↗
PubMed2006

Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material.

The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. Mössbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation.

Adsorption↗
PubMed1988

Interactions of porphyrins with purified DNA and more highly organized structures.

Studies of the solution properties of gold(III)tetrakis(4-N-methylpyridyl) porphine and its DNA binding characteristics have been conducted utilizing uv/vis absorption spectroscopy, circular dichroism (CD), Mossbauer spectroscopy, and temperature-jump relaxation techniques. These studies indicate that over the concentration range considered this water soluble gold(III) porphyrin does not aggregate, binds axial ligands only weakly with a preference for soft Lewis bases, and is capable of intercalation into nucleic acids of appropriate base pair content. The interaction of this and several other porphyrins with the synthetic polynucleotide poly(dA-dC).poly(dT-dG) has been studied. Spectroscopic signatures for intercalation were found for those derivatives not having axial ligands. Intercalation into chromatin in vitro can also occur with those porphyrins and metalloporphyrins which do not have axial ligands. Finally, studies utilizing microinjection techniques indicate that once within the cell, tetrakis(4-N-methylpyridyl)porphine tends to localize in the nucleus.

Animals↗