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PubMed2003

Characterization of diorganotin(IV) complexes with captopril. The first crystallographically authenticated metal complex of this anti-hypertensive agent.

Diorganotin(IV) complexes R(2)Sn(cap) (capH(2)=N-[(S)-3-mercapto-2-methylpropionyl]-L-proline; R=Me, Et, n-Bu and t-Bu) were prepared and characterised. The FTIR and Raman spectra demonstrated that the organotin(IV) moieties interact with the [S] atom of the ligand, while the other coordination sites are the carboxylate and the amide -CO groups. Mössbauer Delta data showed that the diorganotin(IV) compounds adopt slightly distorted trigonal-bipyramidal (tbp) geometry. A single-crystal X-ray study was performed on the compound Me(2)Sn(cap): the Sn atom is five-coordinated in a distorted tbp environment, with two [O] atoms in the axial positions and the [S] and two [C] atoms in the equatorial (eq) plane. Each cap ligand coordinates to two different Sn atoms, and infinite zigzag chains are formed, directed parallel to each other and to the b axis of the unit cell. NMR (CDCl(3)) of the Me(2)Sn(IV) and n-Bu(2)Sn(IV) complexes indicated the presence of different oligomeric species.

Antihypertensive Agents↗

PubMed1998

Diorganotin(IV) complexes of pyridoxal thiosemicarbazone: synthesis, spectroscopic properties and biological activity.

The complexes [SnR2(L)] (R = Me, Et, Bu, Ph; H2L = pyridoxal thiosemicarbazone) have been prepared and characterized. In the light of the spectral properties of the complexes in the solid state (IR, mass, Mössbauer) the bideprotonated thiosemicarbazonato anion is O(phenolic)-, N(3)-, S-bonded to the tin atom which probably has trigonal bipyramidal coordination with N(3) atom and R groups occupying equatorial positions. NMR ( 1H, 13C and 119Sn) data in CDCl3 or DMSO-d6 suggest that this coordinative picture remains in these solutions. The ethyl, butyl and phenyl derivatives suppress proliferation of Friend erithroleukaemia cells (FLC). Of the pyridoxal thiosemicarbazone complexes so far evaluated. [SnBu2(L)] and [SnPh2(L)] showed the lowest thresholds for inhibition of FLC proliferation. The effects of these compounds on DMSO-induced differentiation of FLC, DNA synthesis and reverse transcriptase were also assayed.

Animals↗

PubMed1998

The bidirectional effect of vanadyl ion on the oxygen affinity of human hemoglobin.

The bidirectional effects of vanadyl on the oxygen affinity of hemoglobin depend on the mole ratio of vanadyl to Hb(R). In low R, the vanadyl ion increases Hb's oxygen affinity due to DPG hydrolysis. The lowered oxygen affinity in higher R is mainly due to the reactive-oxygen-species, probably superoxide, induced oxidation of Fe(II)-Hb to Fe(III)-Hb. The conformation change due to vanadyl binding contribute also to the lowered oxygen binding, but is monotonously decreasing with increasing of R values.

Circular Dichroism↗

PubMed1998

Interaction of Et2SnCl2 with 5'-IMP and 5'-GMP.

The interactions of Et2SnCl2 with 5'-IMP and 5'-GMP have been studied in aqueous solutions by 1H- and 31P-NMR spectroscopy as a function of pH. At low pH values (< 4.0) Sn(IV) interacts with the pyrophosphate oxygens of these nucleotides. At intermediate pH values (4-9.5) no interaction of the metal with the nucleotides take place, while at pH > 9.5 the sugar O'2 and O'3 atoms are the preferred coordination sites. In addition, the solid adducts obtained from aqueous solutions at pH = 3-4 of the above interactions correspond to formulae; (Et2Sn)2(5'-IMP)2(H2O) and (Et2Sn)3(5'-GMP)2(OH)2(H2O)2 as their elemental analysis show. IR spectra and solid state 13C, 31P-NMR spectra 119Sn Mössbauer and solution 119Sn-NMR spectra once more confirm the pyrophosphate involvement in bonding with Sn(IV) in oligomeric or polymeric structures and trigonal bipyramidal or octahedral geometries.

Guanosine Monophosphate↗

PubMed1999

Comparison of the core size distribution in iron dextran complexes using Mössbauer spectroscopy and X-ray diffraction.

Mössbauer spectra of a series of iron dextran complexes in the intermediate temperature range where both sextet and doublet coexist may be used to obtain a qualitative description of the distribution of core sizes in these samples. Eight samples from five suppliers have been examined at 100 and 77 K. These differ markedly in the relative doublet contribution to the total spectral area and also in the hyperfine fields characterizing the sextets. The results indicate three distinct types of distribution. One sample from each type has also been examined at 4 K, where the doublet component has vanished and the hyperfine field distribution has become narrow and symmetric. These data are compared with estimates of average core diameters from X-ray line broadening.

Iron-Dextran Complex↗

PubMed2000

Generation of oxoiron (IV) tetramesitylporphyrin pi-cation radical complexes by m-CPBA oxidation of ferric tetramesitylporphyrin derivatives in butyronitrile at - 78 degrees C. Evidence for the formation of six-coordinate oxoiron (IV) tetramesitylporphyrin pi-cation radical complexes FeIV = O(tmp*)X (X = Cl-, Br-), by Mössbauer and X-ray absorption spectroscopy.

The generation of six-coordinate oxoiron (IV) tetramesitylporphyrin pi-caption radical complexes by m-CPBA (meta-chloroperbenzoic acid) oxidation of ferric tetramesitylporphyrin derivatives in butyronitrile at - 78 degrees C was investigated. UV-Vis and EPR spectroscopies indicate that the axial ligand present in the ferric starting derivatives is retained in the high-valent iron complexes. Indirect evidence for the formation of six-coordinate oxoiron (IV) tetramesitylporphyrin complexes FeIV = O(tmp*)X (X=Cl-, Br-) by m-CPBA oxidation of FeX(tmp) (X=Cl-, Br-) in butyronitrile at - 78 degrees C was also obtained by Mössbauer spectroscopy. Direct confirmation of the presence of a halide ion as second axial ligand of iron in these high-valent iron species was obtained by X-ray absorption spectroscopy. The EXAFS spectra of the samples obtained by m-CPBA oxidation of FeX(tmp) (X=Cl-, Br-) were refined using two different coordination models including both four porphyrinato-nitrogens and the axial oxo group. The two models include (model I) or exclude (model II) the axial halogen. The statistical tests indicate the presence of a halide ion as second axial ligand of iron in both derivatives. The refinements led to the following bond distances: FeIV=O(tmp*)Cl(3):Fe-O=1.66(1),Fe-Cl=2.39(2) and Fe-Np=1.99(1) A;FeIV=O(tmp*)Br(4):Fe-O=1.65(1),Fe-Br=2.93(2), Fe-Np=2.02(1) A. The lengthening of the Fe-X(X=Cl-, Br-) distances relative to those occurring in the ferric precursor porphyrins is, most probably, related to the strong trans influence of the oxoiron(IV) fragment present in 3 or 4.

Chlorobenzoates↗

PubMed2000

Does the haemosiderin iron core determine its potential for chelation and the development of iron-induced tissue damage?

Haemosiderin, the major iron storage protein in tissues of iron-loaded tissues shows heterogeneity with respect to both its iron mineralisation product and associated protein. Such mineralisation products have been characterised by a variety of physical techniques including Mössbauer spectroscopy, electron diffraction and EXAFS, and are closely related to the mineral ferrihydrite. A wide range of iron chelators are being developed for the treatment of abnormal haemoglobinopathies, predominantly beta-thalassaemia, which may show greater chelator efficacy for particular mineralisation products of haemosiderin. Even though the tissue iron loadings achieved in different iron-loading syndromes are similar, e.g. naturally occurring iron loading, genetic haemochromatosis and thalassaemia, it is clear that the iron loading in thalassaemic causes extensive damage. The explanation for this could relate to the distribution of iron within different cell types, predominantly reticuloendothelial, its rate of deposition and the mineralisation product of its haemosiderin iron core, goethite.

Animals↗

PubMed2000

Nanoscale iron(III) oxyhydroxy aggregates formed in the presence of functional water-soluble polymers: models for iron(III) biomineralisation processes.

Superparamagnetic clusters of iron(III) oxyhydroxide in the form of poorly crystalline ferrihydrite (formally, 5Fe2O3 x 9H2O) have been synthesised in the presence of the polymers polyvinyl alcohol (PVA), polyacrylic acid (PAA) and alginic acid. The solutions have been characterised by viscosity studies and the resultant arrays isolated from these solutions have been imaged under an electron microscope and their magnetic properties determined by 57Fe-Mössbauer spectroscopic studies at 293 and 77 K and magnetisation measurements at 293 and 5 K. The magnetic data show that the iron(III) oxyhydroxy particles are superparamagnetic. All preparations show hysteretic behaviour with coercive fields being approximately half or less than half of that of ferrihydrite (3.4 kOe) and values of magnetic moment per iron particle less than that of ferrihydrite. Nanoscale aggregates (2-4 nm) are formed in the presence of PVA and PAA while, with alginic acid, extended branch-like structures are observed, their formation being facilitated by the comparatively rigid polysaccharide chain, a process related to iron biomineralisation in diverse biological systems.

Acrylic Resins↗

PubMed2000

Redox properties of iron-dithiocarbamates and their nitrosyl derivatives: implications for their use as traps of nitric oxide in biological systems.

While the Fe(2+)-dithiocarbamate complexes have been commonly used as NO traps to estimate NO production in biological systems, these complexes can undergo complex redox chemistry. Characterization of this redox chemistry is of critical importance for the use of this method as a quantitative assay of NO generation. We observe that the commonly used Fe(2+) complexes of N-methyl-D-glucamine dithiocarbamate (MGD) or diethyldithiocarbamate (DETC) are rapidly oxidized under aerobic conditions to form Fe(3+) complexes. Following exposure to NO, diamagnetic NO-Fe(3+) complexes are formed as demonstrated by the optical, electron paramagnetic resonance and gamma-resonance spectroscopy, chemiluminescence and electrochemical methods. Under anaerobic conditions the aqueous NO-Fe(3+)-MGD and lipid soluble NO-Fe(2+)-DETC complexes gradually self transform by reductive nitrosylation into paramagnetic NO-Fe(2+)-MGD complexes with yield of up to 50% and the balance is converted to Fe(3+)-MGD and nitrite. In dimethylsulfoxide this process is greatly accelerated. More efficient transformation of NO-Fe(3+)-MGD into NO-Fe(2+)-MGD (60-90% levels) was observed after addition of reducing equivalents such as ascorbate, hydroquinone or cysteine or with addition of excess Fe(2+)-MGD. With isotope labeling of the NO-Fe(3+)-MGD with (57)Fe, it was shown that these complexes donate NO to Fe(2+)-MGD. NO-Fe(3+)-MGD complexes were also formed by reversible oxidation of NO-Fe(2+)-MGD in air. The stability of NO-Fe(3+)-MGD and NO-Fe(2+)-MGD complexes increased with increasing the ratio of MGD to Fe. Thus, the iron-dithiocarbamate complexes and their NO derivatives exhibit complex redox chemistry that should be considered in their application for detection of NO in biological systems.

Dimethyl Sulfoxide↗

PubMed2001

The preparation of magnetic proteinaceous microspheres using the sonochemical method.

Using high-intensity ultrasound, we have developed a method for the synthesis of magnetic microspheres. The microspheres are composed of iron oxide-filled and coated globular bovine serum albumin (BSA). The magnetic microspheres are prepared from BSA and iron pentacarbonyl, or from BSA and iron acetate. Transmission electron microscopy and scanning electron microscopy show spherical particles. The particle size distributions are gaussian, with a mean diameter of a few micrometers. Using chemical analysis, it was found that the total percentage of iron oxide in the microspheres is between 39% and 42%. Mössbauer measurements were also performed.

Ferric Compounds↗

PubMed2001

Acetylphenylhydrazine induced haemoglobin oxidation in erythrocytes studied by Mössbauer spectroscopy.

The oxidative action of acetylphenylhydrazine (APH) on red blood cells obtained from healthy donors and from patients with breast cancer has been investigated by Mössbauer spectroscopy. Whole blood was incubated with APH for different time periods and the Mössbauer spectra of the packed red cells were recorded and compared. The evolution with time of the oxidation products has been followed. The largest difference in red cells analysis between healthy persons and patients was found after about 50 min of treatment where Mössbauer spectra of patient samples show a much broader spectral pattern due to an advanced haemoglobin oxidation.

Breast Neoplasms↗

PubMed1997

Crystal size and properties of superparamagnetic iron oxide (SPIO) particles.

The properties of a superparamagnetic iron oxide (SPIO) model contrast agent have been studied. The test material, HEP-SPIO, contained iron oxide multicrystal agglomerates coated with heparin, polyanionic, naturally occurring glycosaminoglycan. Fractionation of the HEP-SPIO suspension showed the existence of colloidally stable particles ranging from approx. 100 nm down to single crystal sizes. The small (< 20 nm) particles represented the major number fraction of particles present, but only approx. 2% of the total iron oxide mass. The volume weighted average diameter of the individual iron oxide crystals forming the multicrystal agglomerates was found to be 11-12 nm using transmission electron microscopy and vibrating sample magnetometry (VSM) techniques. Comparable results were obtained with X-ray diffraction and Mössbauer spectroscopy. A number of additional SPIO properties could also be determined on a routine VSM, such as the distribution standard deviation for the log-normal distribution of crystal sizes, the magnetic susceptibility, the magnetic remanence, and the intrinsic magnetization (magnetic moment) of the iron oxide. These parameters are useful tools for evaluation of the magnetic characteristics and contrast efficacy of SPIO contrast agents.

Chemical Fractionation↗

PubMed1998

The form of iron oxide deposits in thalassemic tissues varies between different groups of patients: a comparison between Thai beta-thalassemia/hemoglobin E patients and Australian beta-thalassemia patients.

Mössbauer spectra of 12 beta-thalassemia/hemoglobin E spleen samples from Thai patients who had not received multiple blood transfusions and chelation therapy and seven beta-thalassemia spleen samples from Australian patients who had received multiple blood transfusions and chelation therapy were recorded with sample temperatures of 78 K. Each spectrum was found to consist of a superposition of a relatively intense central doublet characteristic of high-spin Fe(III), a low intensity sextet of peaks due to magnetic hyperfine-field splitting, and occasionally a doublet that could be attributed to heme iron. A significant (P=0.01) difference (Kolmogorov-Smirnov statistic of 0.71) between the distributions of sextet signal intensity as a fraction (Fs) of the total non-heme iron Mössbauer spectral signal for the two groups of patients was detected. The distribution of Fs for the Thai beta-thalassemia/hemoglobin E spleens had a mean value of 0.128 (S.D. 0.035) while that for the Australian beta-thalassemia spleens had a mean of 0.27 (S.D. 0.12). No significant difference between the distributions of non-heme iron concentrations in the tissues for the two groups of patients was detected by atomic absorption spectrometry. This study shows that the Australian beta-thalassemia patients had a higher fraction of their non-heme spleen iron in a goethite-like form than the Thai beta-thalassemia/Hb E patients.

Chelation Therapy↗

PubMed1999

The effect of prolonged iron loading on the chemical form of iron oxide deposits in rat liver and spleen.

Female Porton rats were loaded with iron either by supplementing the diet with 2.5% carbonyl iron for up to 22 months (18 rats) or by regularly injecting rat blood cells intraperitoneally for up to 10 months (eight rats). 57Fe Mössbauer spectroscopy of freeze-dried samples of liver and spleen was used to analyse the chemical forms of iron deposited in these tissues over the period of iron loading. A sextet signal in the Mössbauer spectra was identified as being due to a form of haemosiderin based on the structure of the mineral goethite. The spectral parameters of the sextet signal in the rat tissues indicate that the goethite-like haemosiderin particles are less crystalline than those found in iron-loaded human tissues. For the dietary-iron-loaded rat livers, the fraction (Fs) of the Mössbauer signal in the form of this sextet was found to increase significantly (from approx 0.04 to 0.09) with the age of the rats (r=0.77, P<0.0005). This indicates that the fraction of liver iron in the form of the goethite-like haemosiderin increases with age of the rat and hence with the duration of iron loading. In addition, Fs for these livers was found to increase significantly with the fraction of iron in non-parenchymal cells as measured by computer-assisted morphometric analysis of histological sections (r=0.71, P<0.005).

Animals↗

PubMed2000

Low-frequency low-field magnetic susceptibility of ferritin and hemosiderin.

Low-frequency low-field magnetic susceptibility measurements were made on four samples of mammalian tissue iron oxide deposits. The samples comprised: (1) horse spleen ferritin; (2) dugong liver hemosiderin; (3) thalassemic human spleen ferritin; and (4) crude thalassemic human spleen hemosiderin. These samples were chosen because Mössbauer spectroscopic measurements on the samples indicated that they exemplified the variation in magnetic and mineral structure found in mammalian tissue iron oxide deposits. The AC-magnetic susceptometry yielded information on the magnetization kinetics of the four samples indicating samples 1, 2, and 3 to be superparamagnetic with values of around 10(11) s(-1) for the pre-exponential frequency factor in the Néel-Arrhenius equation and values for characteristic magnetic anisotropy energy barriers in the range 250-400 K. Sample 4 was indicated to be paramagnetic at all temperatures above 1.3 K. The AC-magnetic susceptometry data also indicated a larger magnetic anisotropy energy distribution in the dugong liver sample compared with samples 1 and 3 in agreement with previous Mössbauer spectroscopic data on these samples. At temperatures below 200 K, samples 1-3 exhibited Curie-Weiss law behavior, indicating weak particle-particle interactions tending to favor antiparallel alignment of the particle magnetic moments. These interactions were strongest for the dugong liver hemosiderin, possibly reflecting the smaller separation between mineral particles in this sample. This is the first magnetic susceptometry study of hemosiderin iron deposits and demonstrates that the AC-magnetic susceptometry technique is a fast and informative method of studying such tissue iron oxide deposits.

Animals↗

PubMed2002

Synthesis, characterization and antitumor studies of Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of N-salicyloyl-N'-o-hydroxythiobenzhydrazide.

A new ligand N-salicyloyl-N'-o-hydroxythiobenzhydrazide (H2Sotbh) forms complexes [Mn(HSotbh)2], [Fe(Sotbh-H)(H2O)2], [M(Sotbh)] [M=Co(II), Cu(II) and Zn(II)] and [Ni(Sotbh)(H(2)O)2], which were characterized by various physico-chemical techniques. Mössbauer spectrum of [Fe(Sotbh-H)(H2O)2] reveals the quantum admixture of 5/2 and 3/2 spin-states. Mn(II), Cu(II) and Ni(II) complexes were observed to inhibit the growth of tumor in vitro, whereas, Fe(III), Co(II), Zn(II) complexes did not. In vivo administration of Mn(II), Cu(II) and Ni(II) resulted in prolongation of survival of tumor bearing mice. Tumor bearing mice administered with Mn(II), Cu(II) and Ni(II) complexes showed reversal of tumor growth associated induction of apoptosis in lymphocytes. The paper discusses the possible mechanisms and therapeutic implication of the H2Sotbh and its metal complexes in tumor regression and tumor growth associated immunosuppression.

Animals↗

PubMed2000

Mössbauer studies on laser evaporated iron atoms and their reactions with oxygen in argon matrices.

Laser-evaporated iron atoms were isolated in low-temperature Ar matrices and their chemical reactions with oxygen were investigated by means of Mössbauer spectroscopy. Reactions of iron atoms with oxygen produce FeO, Fe(O2), FeO3, (O2)FeO2 and OFeO isolated in the Ar matrices and their yields vary depending on the concentration of oxygen. Similarly, FeO and Fe(O2) were obtained by the reaction of iron atoms with N2O. Infrared spectroscopy and molecular orbital calculations were applied to support their assignments.

Calorimetry↗

PubMed2003

Quantum chemical calculations of spectroscopic properties of metalloproteins and model compounds: EPR and Mössbauer properties.

Recently developed theoretical methods to predict EPR and Mössbauer parameters open the way for close interactions between theorists and experimentalists to elucidate the geometric and electronic structures of metalloenzymes and model complexes and to obtain insight into their reactive properties. Spectral calculations (g-values, hyperfine couplings, zero-field splittings, isomer shifts and quadrupole splittings) are also a means to validate theoretical approaches and therefore complement the prediction of geometries, reaction energies and transition states.

Electron Spin Resonance Spectroscopy↗