Clemens Pietzonka

Novel magnetic iron oxide nanoparticles coated with poly(ethylene imine)-g-poly(ethylene glycol) for potential biomedical application: synthesis, stability, cytotoxicity and MR imaging

Magnetic iron oxide nanoparticles have found application as contrast agents for magnetic resonance imaging (MRI) and as switchable drug delivery vehicles. Their stabilization as colloidal carriers remains a challenge. The potential of poly(ethylene imine)-g-poly(ethylene glycol) (PEGPEI) as stabilizer for iron oxide (γ-Fe₂O₃) nanoparticles was studied in comparison to branched poly(ethylene imine) (PEI). Carrier systems consisting of γ-Fe₂O₃-PEI and γ-Fe₂O₃-PEGPEI were prepared and characterized regarding their physicochemical properties including magnetic resonance relaxometry. Colloidal stability of the formulations was tested in several media and cytotoxic effects in adenocarcinomic epithelial cells were investigated. Synthesized γ-Fe₂O₃ cores showed superparamagnetism and high degree of crystallinity. Diameters of polymer-coated nanoparticles γ-Fe₂O₃-PEI and γ-Fe₂O₃-PEGPEI were found to be 38.7 ± 1.0 nm and 40.4 ± 1.6 nm, respectively. No aggregation tendency was observable for γ-Fe₂O₃-PEGPEI over 12 h even in high ionic strength media. Furthermore, IC₅₀ values were significantly increased by more than 10-fold when compared to γ-Fe₂O₃-PEI. Formulations exhibited r₂ relaxivities of high numerical value, namely around 160 mM⁻¹ s⁻¹. In summary, novel carrier systems composed of γ-Fe₂O₃-PEGPEI meet key quality requirements rendering them promising for biomedical applications, e.g. as MRI contrast agents.

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.

Structure and Properties of γ-Brass-Type Pt2Zn11—δ (0.2 < δ < 0.3)†

The γ-brass type phase Pt2Zn11—δ (0.2 2σ (Io) for 293 symmetrically independent intensi ties and 19 variables. The structure consists of a 26 atom cluster which is comprised of four crystallographically distinct atoms. The atoms Zn(1), Pt(1), Zn(2) and Zn(3) form an inner tetrahedron IT, an outer tetrahedron OT, an octahedron OH, and a distorted cuboctahedron CO respectively. About 14 % of the Zn(1) sites are unoccupied. Pt2Zn10.73 melts at 1136(2) K. It is a moderate metallic conductor (ρ298 = 0.2—0.9 mΩ cm) whose magnetic properties (χmol = —4.6 10—10 to —5.4 10—10 m3 mol—1) are dominated by the core diamagnetism of its components. Struktur und Eigenschaften von Pt2Zn11—δ (0.2 < δ < 0.3) vom γ-Messing-Typ Die Phase Pt2Zn11-δ (0.2 2σ (Io), 293 symmetrisch unabhangigen Reflexen und 19 Variablen. Charakteristische Baugruppe der Struktur ist ein 26-Atom-Cluster, der aus vier kristallographisch unterschiedlichen Atomen aufgebaut ist. Die Atome Zn(1), Pt(1), Zn(2) und Zn(3) bilden ein inneres Tetraeder IT, ein auseres Tetraeder OT, ein Oktaeder OH beziehungsweise ein verzerrtes Kuboktaeder CO. Die Zn(1)-Lage ist zu etwa 14 % unterbesetzt. Pt2Zn10.73 schmilzt bei 1136(2) K. Die Verbindung ist ein masiger metallischer Leiter (ρ298 = 0.2—0.9 mΩ cm), dessen magnetische Eigenschaften (χmol = —4.6 10—10 to —5.4 10—10 m3 mol—1) vom Diamagnetismus der Atomrumpfe der Komponenten bestimmt werden.

Field effects in alkali ion emitters: Transition from Langmuir–Child to Schottky regime

The thermionic emission of potassium and cesium ions from Leucite type materials has been investigated as a function of temperature and electric field across the surface. The temperature dependence reveals classical Richardson–Dushman behavior. For small electric fields (typically smaller than 1000 V/cm) applied orthogonal to the emitter surface, the emitted ion density follows the Langmuir–Child law. The ion density follows Schottky behavior at higher electric fields (typically larger than 2000 V/cm). The cross over is interpreted in terms of a transition from space-charge limited ion emission to one limited by the effective work function for ion emission.

Self-organization of multifunctional surfaces--the fingerprints of light on a complex system.

Nanocomposite patterns and nanotemplates are generated by a single-step bottom-up concept that introduces laser-induced periodic surface structures (LIPSS) as a tool for site-specific reaction control in multicomponent systems. Periodic intensity fluctuations of this photothermal stimulus inflict spatial-selective reorganizations, dewetting scenarios and phase segregations, thus creating regular patterns of anisotropic physicochemical properties that feature attractive optical, electrical, magnetic, and catalytic properties.

Crystal and magnetic spin structure of Germanium-Hedenbergite, CaFeGe2O6, and a comparison with other magnetic/magnetoelectric/multiferroic pyroxenes

Abstract CaFeGe2O6, the germanium-analogue to the mineral Hedenbergite, has been synthesized at 1273 K in evacuated SiO2-glass-tubes. Powder neutron diffraction data collected between 4 K and 300 K were used to evaluate the magnetic spin as well as the nuclear crystal structure and its T-evolution. CaFeGe2O6 is monoclinic, C2/c, a = 10.1778(5) Å, b = 9.0545(4) Å, c = 5.4319(3) Å, β = 104.263(3)°, Z = 4 at room temperature. No change of symmetry was observed down to 4 K. Below 43 K, additional magnetic Bragg reflections appear, which can be indexed on the basis of a commensurate magnetic propagation vector k [1, 0, 0]. The successful description of the magnetic spin structure reveals a ferromagnetic spin coupling within the Fe2+O6 M1 chains, while the coupling between the chains is antiferromagnetic. Spins are oriented collinearly within the a–c plane and form an angle of ∼60° with the crystallographic a-axis. The magnetic moment at 4 K amounts to about 4.4 μB. The observed magnetic structure is similar to that of other Ca-clinopyroxenes. The present data are put into context with the structural and magnetic properties of other pyroxenes – among them magnetoelectric and multiferroic pyroxene-type compounds.

Magnetic and low-temperature structural behavior of clinopyroxene-type FeGeO3: A neutron diffraction, magnetic susceptibility, and 57Fe Mössbauer study

Abstract The clinopyroxene-type compound FeGeO3 was synthesized using ceramic sintering techniques at 1273 K in evacuated silica tubes and investigated by powder neutron diffraction between 4 and 300 K, X-ray diffraction, SQUID magnetometry, and 57Fe Mössbauer spectroscopy. The title compound shows space group C2/c symmetry (high pressure, HP-topology) between 4 and 900 K. No structural phase transition is present within this temperature interval, whereas lattice parameters show discontinuities around 50 and 15 K, which are due to magnetic phase transitions and the associated magneto-elastic coupling of the lattice. The magnetic susceptibility data show two maxima in their temperature dependence, one at ~47 K, the second around 12 K (depending on the external field), indicative of two magnetic transitions in the title compound. Neutron data shows that for T < 45 K, FeGeO3 orders magnetically, having a simple collinear structure, with space group C2/c, and with the spins aligned parallel to the crystallographic b-axis, both on M1 and M2. The coupling within the M1/M2 band is ferromagnetic, whereas between them it is antiferromagnetic. As the bulk magnetic measurements in the paramagnetic state revealed a dominating ferromagnetic coupling, the intra-chain interactions dominate the inter-chain interaction. At 12 K, additional magnetic reflections appear, revealing a second magnetic phase transition. Spins are rotated away from the b-axis toward the a-c plane. The coupling within the M1 chain is still ferromagnetic and antiferromagnetic between the M1 chains. However, spins on M1 and M2, are no longer collinear. The moment on the M2 site is rotated further away from the b-axis than on M1.

Pseudohalogenido complexes of iron-2,2′-bidipyrrins

The chlorido iron(III) complex of octaethyl-2,2′-bidipyrrin has been transformed to a series of pseudohalide complexes by ligand exchange reactions with azide, cyanate, thiocyanate and selenocyanate anions. All new complexes show the expected N-coordination of the axial ligand to the iron(III) center. In the solid state, all four species display an intermediate spin (S = 3/2) ground state, with a gradual increase of a high spin (S = 5/2) contribution at elevated temperatures for the members with the smallest ligand field strengths, i.e. the cyanato and the azido derivatives. In solution, proton NMR, and in particular IR spectroscopic studies support the interpretation of a high-spin state at ambient temperature throughout the series. The dependency of the spin state on the crystalline or dissolved state thus resembles that found for a similar series of halide derivatives before. In dichloromethane solution, the thiocyanato and selenocyanato complexes are very sensitive to aerial oxidation, forming oxacorrole and thiacorrole complexes as the only isolated products. These complexes show a S = 3/2 spin state in the solid as well as in solution, and their structural analyses prove the expected strong π-binding of the linear pseudohalide ion to the iron(III) central metal.

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.

Ru9Zn7Sb8: a structure with a 2 × 2 × 2 supercell of the half-Heusler phase.

The title compound Ru(9)Zn(7)Sb(8) was synthesized via a high-temperature reaction from the elements in a stoichiometric ratio, and its structure was solved by a single-crystal X-ray diffraction method. The structure [cubic, space group Fm3m, Pearson symbol cF96, a = 11.9062(14) Å (293 K), and Z = 4] adopts a unique 2a(hh) × 2a(hh) × 2a(hh) supercell of a normal half-Heusler phase and shows abnormal features of atomic coordination against the Pauling rule. The formation of this superstructure was discussed in light of the valence electron concentration per unit cell. It is a metallic conductor [ρ(300 K) = 16 μΩ·m], and differential scanning calorimetry revealed that Ru(9)Zn(7)Sb(8) undergoes a transformation at 1356(1) K and melts, by all indications, congruently at 1386 K. At room temperature, its thermal conductivity is about 3 W/m·K, which is only one-quarter of that of most normal half-Heusler phases. Ru(9)Zn(7)Sb(8) as well as its analogues of iron-, cobalt-, rhodium-, and iridium-containing compounds are expected to serve as a new structure type for exploring new thermoelectric materials.