A Unique Mechanochemical Redox Reaction Yielding Nanostructured Double Perovskite Sr2FeMoO6 With an Extraordinarily High Degree of Anti-Site Disorder.

Strontium ferromolybdate, Sr2FeMoO6, is an important member of the family of double perovskites with the possible technological applications in the field of spintronics and solid oxide fuel cells. Its preparation via a multi-step ceramic route or various wet chemistry-based routes is notoriously difficult. The present work demonstrates that Sr2FeMoO6 can be mechanosynthesized at ambient temperature in air directly from its precursors (SrO, α-Fe, MoO3) in the form of nanostructured powders, without the need for solvents and/or calcination under controlled oxygen fugacity. The mechanically induced evolution of the Sr2FeMoO6 phase and the far-from-equilibrium structural state of the reaction product are systematically monitored with XRD and a variety of spectroscopic techniques including Raman spectroscopy, 57Fe Mössbauer spectroscopy, and X-ray photoelectron spectroscopy. The unique extensive oxidation of iron species (Fe0 → Fe3+) with simultaneous reduction of Mo cations (Mo6+ → Mo5+), occuring during the mechanosynthesis of Sr2FeMoO6, is attributed to the mechanically triggered formation of tiny metallic iron nanoparticles in superparamagnetic state with a large reaction surface and a high oxidation affinity, whose steady presence in the reaction mixture of the milled educts initiates/promotes the swift redox reaction. High-resolution transmission electron microscopy observations reveal that the mechanosynthesized Sr2FeMoO6, even after its moderate thermal treatment at 923 K for 30 min in air, exhibits the nanostructured nature with the average particle size of 21(4) nm. At the short-range scale, the nanostructure of the as-prepared Sr2FeMoO6 is characterized by both, the strongly distorted geometry of the constituent FeO6 octahedra and the extraordinarily high degree of anti-site disorder. The degree of anti-site disorder ASD = 0.5, derived independently from the present experimental XRD, Mössbauer, and SQUID magnetization data, corresponds to the completely random distribution of Fe3+ and Mo5+ cations over the sites of octahedral coordination provided by the double perovskite structure. Moreover, the fully anti-site disordered Sr2FeMoO6 nanoparticles exhibit superparamagnetism with the blocking temperature T B = 240 K and the deteriorated effective magnetic moment µ = 0.055 µ B per formula unit.

Exchange Bias in FePt-FePt3 Thin Films by Controlled Phase Transition of Blended Nanoparticle Building Blocks.

Nanostructured composite thin films showing magnetic exchange coupling at the material interface have attracted great interest for the development of electronic components such as spin-valves. Besides the commonly performed fabrication of multilayer systems, the utilization of nanoparticle building blocks holds great potential for thin films with tailored magnetic properties and allows the facile but controlled combination of materials with complementary magnetic characteristics. In this work, we present the use of prefabricated highly crystalline iron platinum (fcc-FePt) and iron oxide (FexOy) nanoparticles for the preparation of nanocomposite thin films with varying compositions by wet processing from mixed dispersions. The resulting multiphase coatings showed high homogeneity, low surface roughness, and superparamagnetic behavior. By the variation of the amount of incorporated iron oxide, a precise adjustment of the magnetization at high field strength could be achieved. Furthermore, calcination under inert gas atmosphere resulted in a controlled phase transition of the magnetic phases and thus, in purely metallic coatings composed of ferromagnetic fct-FePt and antiferromagnetic fcc-FePt3, a decrease in surface roughness as well as high magnetic coercivity at room temperature. Field-cooling below the Néel temperature of fcc-FePt3 led to an exchange bias effect with a strong increase in coercivity and the characteristic hysteresis shift. In comparison to the literature, our nanocomposite thin films showed fully ordered phases without the occurrence of phase impurities, a distinctly higher coercivity, and an exchange bias shift of 38.7 mT.

Non-Aqueous Sol-Gel Synthesis of FePt Nanoparticles in the Absence of In Situ Stabilizers.

The synthesis of FePt nanocrystals is typically performed in an organic solvent at rather high temperatures, demanding the addition of the in situ stabilizers oleic acid and oleylamine to produce monomodal particles with well-defined morphologies. Replacing frequently-used solvents with organic media bearing functional moieties, the use of the stabilizers can be completely circumvented. In addition, various morphologies and sizes of the nanocrystals can be achieved by the choice of organic solvent. The kinetics of particle growth and the change in the magnetic behavior of the superparamagnetic FePt nanocrystals during the synthesis with a set of different solvents, as well as the resulting morphologies and stoichiometries of the nanoparticles were determined by powder X-ray diffraction (PXRD), small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP-OES)/mass spectrometry (ICP-MS), and superconducting quantum interference device (SQUID) measurements. Furthermore, annealing of the as-prepared FePt nanoparticles led to the ordered L10 phase and, thus, to hard magnetic materials with varying saturation magnetizations and magnetic coercivities.

Short term storage stability at room temperature of two different platelet-rich plasma preparations from equine donors and potential impact on growth factor concentrations.

BACKGROUND: The increasing interest in platelet-rich plasma (PRP) based therapies is as yet accompanied by inconsistent information regarding nearly all aspects of handling and application. Among these storage stability of processed platelet-rich products may be the basis for a more flexible application mode. The objective of this study was (1) to estimate the storage stability of growth factors platelet derived growth factor BB (PDGF-BB) and transforming growth factor ß1 (TGF-ß1) in both, a single-step softspin centrifugation-based pure-PRP (P-PRP, ACP®), and a gravity filtration system-based leukocyte-rich-PRP (L-PRP, E-PET), over a six hours time span after preparation at room temperature and (2) to identify possible factors influencing these growth factor concentrations in an equine model. RESULTS: Growth factor concentrations remained stable over the entire investigation period in L-PRP as well as P-PRP preparations revealing a mean of 3569 pg/ml PDGF-BB for E-PET and means of 1276 pg/ml PDGF-BB and 5086 pg/ml TGF-ß1 for ACP®. Pearson correlations yielded no significant impact of whole blood platelet (PLT), white blood cell (WBC) and red blood cell (RBC) counts on resulting cytokine values. In case of ACP® no significant dependencies between PLT, WBC and RBC counts of the processed platelet-rich product and resulting cytokine content occurred with exception of TGF-ß1 concentrations showing a strong correlation with the WBC content. PDGF-BB content of E-PET preparations showed a strong positive correlation with PLT and a strong negative with WBC of these preparations but not with RBC. CONCLUSIONS: L-PRP ad modum E-PET and P-PRP ad modum ACP® are applicable over at least a six hours time span at room temperature without loss of growth factor content. Based on the results of this study factors influencing the resulting growth factor concentrations still remain questionable. Additional studies implicating a further standardization of preparation protocols are necessary to identify consistent impact on cytokine content after PRP processing.

Spin Crossover and Valence Tautomerism in Neutral Homoleptic Iron Complexes of Bis(pyridylimino)isoindolines.

Homoleptic iron complexes of six bis(pyridylimino)isoindoline (bpi) ligands with different substituents (H, Me, Et, tBu, OMe, NMe2) at the 4-positions of the pyridine moieties have been prepared and studied with regard to temperature-dependent spin and redox states by a combination of (57)Fe Mössbauer spectroscopy, SQUID magnetometry, single-crystal X-ray diffraction analysis, X-band EPR, and (1)H NMR spectroscopy. While the H-, methyl-, and ethyl-substituted complexes remain in a pure high-spin state irrespective of the temperature, the 4-tert-butyl-substituted derivative shows spin-crossover behavior. The methoxy- and dimethylamino-substituted compounds were found to easily undergo oxidation. In the crystalline state, valence tautomeric behavior was observed for the methoxy derivative as a thermally activated charge-transfer transition, accompanied by a spin crossover above 200 K. The valence tautomerism leads to a chelate with one of the bpi ligands as a dianion radical L(2-·) and with an effective spin of S=2.

Iron 10-thiacorroles: bioinspired iron(III) complexes with an intermediate spin (S=3/2) ground state.

A first systematic study upon the preparation and exploration of a series of iron 10-thiacorroles with simple halogenido (F, Cl, Br, I), pseudo-halogenido (N3 , I3 ) and solvent-derived axial ligands (DMSO, pyridine) is reported. The compounds were prepared from the free-base octaethyl-10-thiacorrole by iron insertion and subsequent ligand-exchange reactions. The small N4 cavity of the ring-contracted porphyrinoid results in an intermediate spin (i.s., S=3/2) state as the ground state for the iron(III) ion. In most of the investigated cases, the i.s. state is found unperturbed and independent of temperature, as determined by a combination of X-ray crystallography and magnetometry with (1) H NMR-, EPR-, and Mössbauer spectroscopy. Two exceptions were found. The fluorido iron(III) complex is inhomogenous in the solid and contains a thermal i.s. (S=3/2)→high spin (h.s., S=5/2) crossover fraction. On the other side, the cationic bis(pyridine) complex resides in the expected low spin (l.s., S=1/2) state. Chemically, the iron 10-thiacorroles differ from the iron porphyrins mainly by weaker axial ligand binding and by a cathodic shift of the redox potentials. These features make the 10-thiacorroles interesting ligands for future research on biomimetic catalysts and model systems for unusual heme protein active sites.

Mechanosynthesis of nanocrystalline fayalite, Fe2SiO4.

Nanostructured fayalite (α-Fe(2)SiO(4)) with a large volume fraction of interfaces is synthesized for the first time via single-step mechanosynthesis, starting from a 2α-Fe(2)O(3) + 2Fe + 3SiO(2) mixture. The nonequilibrium state of the as-prepared silicate is characterized by the presence of deformed polyhedra in the interface/surface regions of nanoparticles.

A molecular magnet confined in the nanocage of a globular protein.

The effect of confinement and energy transfer on the dynamics of a molecular magnet, known as a model system to study quantum coherence, is investigated. For this purpose the well-known polyoxovanadate [V(15)As(6)O(42)(H(2)O)](6-) (V(15)) is incorporated into a protein (human serum albumin, HSA) cavity. Due to a huge overlap of the optical absorption spectrum of V(15) with the emission spectrum of a fluorescence center of HSA (containing a single tryptophan residue), energy transfer is induced and probed by steady-state and time-resolved fluorescence. The geometrical coordination and the distance of the confined V(15) to the tryptophan moiety of HSA are investigated at various temperatures. This effect is used as a local probe for the thermal denaturation of the protein at elevated temperatures.

Serum thyrotropin levels predict all-cause and circulatory mortality in patients with invasively treated coronary artery disease.

The aim of the present study was to analyze the relation of low or high serum thyrotropin (TSH) with mortality in patients with invasively treated coronary artery disease. We followed-up 942 patients who underwent coronary angioplasties or coronary artery bypass graft surgery over a mean follow-up period of 6.4+/-1.6 years. The study population was divided into three groups using the reference limits of serum TSH (0.25-2.12 mIU/l) as cut-offs. There were 118 patients (12.5%) with low and 125 patients (13.3%) with high serum TSH. One hundred and seventy-four subjects (18.5%) deceased during follow-up. Multivariable analyses revealed that both subjects with low and high serum TSH had a lower all-cause and circulatory mortality than subjects with serum TSH within the reference range. We conclude that low and high serum TSH levels are associated with a reduced all-cause and circulatory mortality in patients with coronary artery disease.

Outcome after coronary artery bypass graft surgery, coronary angioplasty and stenting.

AIMS: We undertook this prospective observational study to investigate the long-term prognosis after balloon angioplasty (PTCA), coronary stenting (CS) and coronary artery bypass grafting (CABG). METHODS AND RESULTS: A total number of 1038 patients with PTCA (n=499), CS (n=294) or CABG (n=245) were followed-up over a mean time of 6.4+/-1.8 years. Forty-two patients (4.0%) were lost to follow-up, leaving a study population of 996 subjects who were available for analyses. The primary and secondary endpoints were mortality and major adverse cardiac events (MACE), respectively. Overall death rate was 19.3%. Age, pulse pressure, smoking, diabetes, serum LDL cholesterol levels and left ventricular ejection fraction rather than the intervention type independently predicted mortality. The incidence rate of MACE was 53.7%. Compared to PTCA patients, CS patients had lower (hazard ratio 0.693; 95% confidence interval 0.514-0.793) and CABG patients the lowest risk of MACE (hazard ratio 0.343; 95% confidence interval 0.261-0.450). Further risk factors for MACE were serum LDL cholesterol levels, three-vessel coronary artery disease and left ventricular ejection fraction of <30%. CONCLUSION: Long-term mortality does not differ among patients who received percutaneous interventions or CABG. Major adverse cardiac events occur more often in patients with previous percutaneous interventions, whereby CS has advantage over PTCA.