Magnetosome Organization in Magnetotactic Bacteria Unraveled by Ferromagnetic Resonance Spectroscopy.

Magnetotactic bacteria form assemblies of magnetic nanoparticles called magnetosomes. These magnetosomes are typically arranged in chains, but other forms of assemblies such as clusters can be observed in some species and genetic mutants. As such, the bacteria have developed as a model for the understanding of how organization of particles can influence the magnetic properties. Here, we use ferromagnetic resonance spectroscopy to measure the magnetic anisotropies in different strains of Magnetosprillum gryphiswaldense MSR-1, a bacterial species that is amendable to genetic mutations. We combine our experimental results with a model describing the spectra. The model includes chain imperfections and misalignments following a Fisher distribution function, in addition to the intrinsic magnetic properties of the magnetosomes. Therefore, by applying the model to analyze the ferromagnetic resonance data, the distribution of orientations in the bulk sample can be retrieved in addition to the average magnetosome arrangement. In this way, we quantitatively characterize the magnetosome arrangement in both wild-type cells and ΔmamJ mutants, which exhibit differing magnetosome organization.

Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity.

Deprotonation of ligand-appended alkoxyl groups in mononuclear copper(II) complexes of N,O ligands L1 and L2 , gave dinuclear complexes sharing symmetrical Cu2 O2 cores. Molecular structures of these mono- and binuclear complexes have been characterized by XRD, and their electronic structures by UV/Vis, 1 H NMR, EPR and DFT; moreover, catalytic performance as models of catechol oxidase was studied. The binuclear complexes with anti-ferromagnetically coupled copper(II) centers are moderately active in quinone formation from 3,5-di-tert-butyl-catechol under the established conditions of oxygen saturation, but are strongly activated when additional dioxygen is administered during catalytic turnover. This unforeseen and unprecedented effect is attributed to increased maximum reaction rates vmax , whereas the substrate affinity KM remains unaffected. Oxygen administration is capable of (partially) removing limitations to turnover caused by product inhibition. Because product inhibition is generally accepted to be a major limitation of catechol oxidase models, we think that our observations will be applicable more widely.

Tetrabromidocuprates(II)-Synthesis, Structure and EPR.

Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several "onium" cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g‖ and g⊥) of the tensors could be determined and information on the structural changes in the [CuBr4](2-) anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.

Robust Cluster Building Unit: Icosanuclear Heteropolyoxocopperate Templated by Carbonate.

The encapsulation of carbonate derived from atmospheric CO2 has resulted in an icosanuclear heteropolyoxocopperate, isolated as a metal-organic 1D chain, 2D sheet, or 3D framework, in which the Cu20 nanocluster represents the first eight-capped α-Keggin polyoxometalate with the late-transition-metal Cu(II) as the polyatom, CO3(2-) as the heteroanion, and OH(-) and suc(2-) or glu(2-) (H2suc=succinic acid; H2glu=glutaric acid) as the terminal ligands, which suggests a conceptual similarity to classical polyoxometalates. Even in the presence of competitive SO4(2-) in the assembly system, the CO3(2-) anion is still captured as a template to direct the formation of the Cu20 nanocluster, which indicates the stronger templation ability of CO3(2-) compared with SO4(2-). When other aliphatic dicarboxylates, such as glutaric acid, were used as ligands, the CO3(2-)-templated Cu20 nanocluster was maintained and acted as a cluster building unit (CBU) to be linked by two glutarate bridges to generate a distinct 1D metal-organic chain. This report presents not only a rare example of a huge anion-templated transition-metal cluster, but also its use as a robust CBU to construct novel coordination architectures. Variable-temperature magnetic susceptibility studies revealed that an antiferromagnetic interaction exists within the Cu20 nanocluster. The correlation between the coordination structure and the electron paramagnetic resonance spectra recorded of both powder and single-crystal samples are discussed in detail.

N-2-pyridinylmethyl-N'-arylmethyl-diaminomaleonitriles: new highly selective chromogenic chemodosimeters for copper(II).

Copper chemodosimeters: The copper(II)-promoted air oxidation of 1-3 to form 4-6 permits the highly selective colorimetric detection of Cu(2+) ions. The formation of copper(II) complexes of 4-6 proceeds rapidly, and the chemodosimeters 1-3 are viable at physiological pH.

Tetrachloridocuprates(II)-synthesis and electron paramagnetic resonance (EPR) spectroscopy.

Ionic liquids (ILs) on the basis of metal containing anions and/or cations are of interest for a variety of technical applications e.g., synthesis of particles, magnetic or thermochromic materials. We present the synthesis and the results of electron paramagnetic resonance (EPR) spectroscopic analyses of a series of some new potential ionic liquids based on tetrachloridocuprates(II), [CuCl(4)](2-), with different sterically demanding cations: hexadecyltrimethylammonium 1, tetradecyltrimethylammonium 2, tetrabutylammonium 3 and benzyltriethylammonium 4. The cations in the new compounds were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. The EPR hyperfine structure was not resolved. This is due to the exchange broadening, resulting from still incomplete separation of the paramagnetic Cu(II) centers. Nevertheless, the principal values of the electron Zeemann tensor (g(║) and g(┴)) of the complexes could be determined. Even though the solid substances show slightly different colors, the UV/Vis spectra are nearly identical, indicating structural changes of the tetrachloridocuprate moieties between solid state and solution. The complexes have a promising potential e.g., as high temperature ionic liquids, as precursors for the formation of copper chloride particles or as catalytic paramagnetic ionic liquids.

On the interaction of ascorbic acid and the tetrachlorocuprate ion [CuCl4]2- in CuCl nanoplatelet formation from an ionic liquid precursor (ILP).

The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C(4)Py](2)[CuCl(4)] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl(4)](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl(4)](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.

Temperature dependence of interactions between stable piperidine-1-yloxyl derivatives and a semicrystalline ionic liquid.

The stable 2,2,6,6-tetramethylpiperidine-1-yloxyl and its derivatives with hydrogen-bond-forming (-OH, -OSO(3)H), anionic (-OSO(3) (-) bearing K(+) or [K(18-crown-6)](+) as counter ion), or cationic (-N(+)(CH(3))(3) bearing I(-), BF(4) (-), PF(6) (-) or N(-)(SO(2)CF(3))(2) as counter ion) substituents are investigated in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide over a wide temperature range. The temperature dependence of the viscosity of the ionic liquid is well described by the Vogel-Fulcher-Tammann equation. Interestingly, the temperature dependence of the rotational correlation time of the spin probes substituted with either a hydrogen-bond-forming group or an ionic substituent can be described using the Stokes-Einstein equation. In contrast, the temperature dependence of the rotational correlation time of the spin probe without an additional substituent at the 4-position to the nitroxyl group does not follow this trend. The activation energy for the mobility of the unsubstituted spin probe, determined from an Arrhenius plot of the spin-probe mobility in the ionic liquid above the melting temperature, is comparable with the activation energy for the viscous flow of the ionic liquid, but is higher for spin probes bearing an additional substituent at the 4-position. Quantum chemical calculations of the spin probes using the 6-31G+d method give information about the rotational volume of the spin probes and the spin density at the nitrogen atom of the radical structure as a function of the substituent at the spin probes in the presence and absence of a counter ion. The results of these calculations help in understanding the effect of the additional substituent on the experimentally determined isotropic hyperfine coupling constant.

Influence of imidazolium bis(trifluoromethylsulfonylimide)s on the rotation of spin probes comprising ionic and hydrogen bonding groups.

The influence of the alkyl chain length in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonylimide)s is studied to explore the rotation of piperidine-1-yloxyl derivatives substituted with either hydrogen bonding hydroxy group or ionic substituents, such as the cationic trimethylammonium or the anionic sulfate group placed at the 4 position. Structural variation of the ionic liquids results in differences of their viscosity influencing the rotation of the spin probes. The size of the average rotational correlation times of the spin probes dissolved in the ionic liquids depends further on the additional substituent in 4-position at these spin probes. The rotational correlation time exhibits a linear dependence on the ionic liquid viscosity in the case of the spin probe forming hydrogen bonding with the ionic liquids. In contrast to this, a deviation from the Stokes-Einstein behavior is found in the case of rotation of the charged spin probes in the 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonylimide)s substituted with a longer alkyl chain. This effect may be explained by phase separation on a molecular level between the charged part of the ionic liquid and the longer alkyl chains bound at the imidazolium ion. Although the neutral and the cationic spin probes show only a slight dependence between ionic liquid structure variation and the hyperfine coupling constants, structural effects cause changes in the hyperfine coupling constants in the case of the anionic spin probes. These probes strongly interact with the imidazolium ion.

Temperature dependence of interactions between stable piperidine-1-yloxyl derivatives and an ionic liquid.

2,2,6,6-Tetramethylpiperidine-1-yloxyl derivatives substituted with either hydrogen bonding [-OH, -OSO(3)H] or ionic [-OSO(3) (-)Na(+), -OSO(3) (-)K(+), N(+)(CH(3))(3)I(-), N(+)(CH(3))(3) N(-)(SO(2)-CF(3))(2)] substituents are investigated in 1-butyl-3-methylimidazolium tetrafluoroborate over a wide temperature range covering both glassy and viscous states. The Vogel-Fulcher-Tammann equation describes the temperature dependence of the ionic liquid viscosity. Quantum chemical calculations of the spin probes at the UB3LYP/6-311(2d,p++) level are done to describe the dependence of the spin density on nitrogen on the substitution pattern of the 4-position of the probe. The results of these calculations are also used to understand the experimental results obtained by applying the Spernol-Gierer-Wirtz theory to analyze the viscosity dependence of the rotational correlation time of the spin probes. Significant differences are found between 2,2,6,6-tetramethylpiperidine-1-yloxyl and its derivatives containing substituents that are able to form hydrogen bonds with the ionic liquid. Moreover, derivatives substituted with ionic groups at the 4-position have a large effect on temperature-induced solvent viscosity, as this is particularly dependent on the nature of the substituent at the 4-position. These dependencies include the temperature region that can be used to describe interactions between the spin probes and the ionic liquid, diffusion into the free volume during non-activated (neutral spin probes) and activated (charged spin probes) processes. Additional parameters are the radii of the ionic liquid and the spin probes, which are calculated and measured approximately. In addition, the temperature dependence of the isotropic hyperfine coupling constants of the spin probes results in information about the micropolarity of the ionic liquid. At room temperature, this is comparable to that of the solvent dimethylsulfoxide.

Nonaligned carbon nanotubes anchored on porous alumina: formation, process modeling, gas-phase analysis, and field-emission properties.

We have developed a chemical vapor deposition (CVD) process for the catalytic growth of carbon nanotubes (CNTs), anchored in a comose-type structure on top of porous alumina substrates. The mass-flow conditions of precursor and carrier gases and temperature distributions in the CVD reactor were studied by transient computational fluid dynamic simulation. Molecular-beam quadrupole mass spectroscopy (MB-QMS) has been used to analyze the gas phase during ferrocene CVD under reaction conditions (1073 K) in the boundary layer near the substrate. Field-emission (FE) properties of the nonaligned CNTs were measured for various coverages and pore diameters of the alumina. Samples with more dense CNT populations provided emitter-number densities up to 48,000 cm(-2) at an electric field of 6 V microm(-1). Samples with fewer but well-anchored CNTs in 22-nm pores yielded the highest current densities. Up to 83 mA cm(-2) at 7 V microm(-1) in dc mode and more than 200 mA cm(-2) at 11 V microm(-1) in pulsed diode operation have been achieved from a cathode size of 24 mm2.

Bis(1,2-dithiosquarato)nickelates(II) - Synthesis, Structure, EPR and Thermal Behavior.

1,2-Dithiosquaratonickelates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. The synthesis and characterization, including mass spectrometry, of a series 1,2-dithiosquaratonickelates(II), [Ni(dtsq)2]2-, with several "onium" cations is reported and the X-ray structures of two diamagnetic complexes, (HexPh3N)2[Ni(dtsq)2] and (BuPh3N2[Ni(dtsq)2] with sterically demanding counter ions are presented. The diamagnetic nickel complexes have been doped as host lattices with traces of Cu(II) to measure EPR for additional structural information. The thermal behavior of this series is studied by thermogravimetry and differential thermo analysis (TG/DTA). The thermolysis in air as well as under nitrogen atmosphere of these complexes results in nickel oxide nano-particles in all cases, which are characterized by X-ray powder diffraction.

Mechanical homeostasis of a DOPA-enriched biological coating from mussels in response to metal variation.

Protein-metal coordination interactions were recently found to function as crucial mechanical cross-links in certain biological materials. Mussels, for example, use Fe ions from the local environment coordinated to DOPA-rich proteins to stiffen the protective cuticle of their anchoring byssal attachment threads. Bioavailability of metal ions in ocean habitats varies significantly owing to natural and anthropogenic inputs on both short and geological spatio-temporal scales leading to large variations in byssal thread metal composition; however, it is not clear how or if this affects thread performance. Here, we demonstrate that in natural environments mussels can opportunistically replace Fe ions in the DOPA coordination complex with V and Al. In vitro removal of the native DOPA-metal complexes with ethylenediaminetetraacetic acid and replacement with either Fe or V does not lead to statistically significant changes in cuticle performance, indicating that each metal ion is equally sufficient as a DOPA cross-linking agent, able to account for nearly 85% of the stiffness and hardness of the material. Notably, replacement with Al ions also leads to full recovery of stiffness, but only 82% recovery of hardness. These findings have important implications for the adaptability of this biological material in a dynamically changing and unpredictable habitat.

Synthesis, characterization, DFT studies and catalytic activities of manganese(II) complex with 1,4-bis(2,2':6,2''-terpyridin-4'-yl) benzene.

A new di-manganese complex with "back-to-back" 1,4-bis(2,2':6,2''-terpyridin-4'-yl) benzene ligation has been synthesized and characterised by a variety of techniques. The back-to-back ligation presents a novel new mononuclear manganese catalytic centre that functions as a heterogeneous catalysis for the evolution of oxygen in the presence of an exogenous oxidant. We discuss the synthesis and spectroscopic characterizations of this complex and propose a mechanism for oxygen evolution activity of the compound in the presence of oxone. The di-manganese complex also shows efficient and selective catalytic oxidation of sulfides in the presence of H(2)O(2). Density functional theory calculations were used to assess the structural optimization of the complex and a proposed reaction pathway with oxone. The calculations show that middle benzene ring is distorted respect to both of metallic centers, and this in turn leads to negligible resonance of electrons between two sides of complex. The calculations also indicate the unpaired electron located on oxyl-ligand emphasizes the radical mechanism of water oxidation for the system.

Synthesis of LiyMnSiOx and LiMnPO4 nanostructures.

Nanosized Li(y)MnSiO(x) and LiMnPO(4) have been synthesized by a hydrothermal route. Simply by changing parameters such as metal precursors and/or template, high surface area Li(y)MnSiO(x) with different morphology and sizes were prepared, in particular hollow spheres and plate-like nanoparticles, however with poorly developed crystallinity. In the case of LiMnPO(4), highly crystalline nanocrystals were prepared.

Uniform metal (hydr)oxide particles from water/ionic liquid precursor (ILP) mixtures.

We have recently shown that the hydrated ionic liquid tetrabutylammonium hydroxide (TBAH) is an efficient ionic liquid precursor (ILP) for the fabrication of ZnO/carbohydrate materials (D. Mumalo-Djokic, W. B. Stern, A. Taubert, Cryst. Growth Des. 2008, 8, 330). The current paper shows that ZnO is just one example out of the large group of technologically important metal (hydr)oxides that can be made using TBAH. Simply by using different metal acetates as precursors in TBAH, it is possible to make a wide variety of metal (hydr)oxides with well-defined size, morphology, and chemical composition. It is also possible to dope metal oxide particles or to synthesize mixed metal oxide particles, and therefore to control properties like magnetism.

Structural and analytical studies of silica accumulations in Equisetum hyemale.

Horsetail (Equisetum spp.) is known as one of the strongest accumulators of silicon among higher terrestrial plants. We use the combination of position-resolved analytical techniques, namely microtomography, energy-dispersive X-Ray elemental mapping, Raman microscopy, as well as small-angle and wide-angle scattering of X-rays, to study the type, distribution and nanostructure of silica in the internodes of Equisetum hyemale. The predominant silicification pattern is a thin continuous layer on the entire outer epidermis with the highest density in particular knob regions of the long epidermal cells. The knob tips contain up to 33 wt% silicon in the form of pure hydrated amorphous silica, while the silica content is lower in the inner part of the knobs and on the continuous layer. In contrast to the knob tips, the silica in these regions lacks silanol groups and is proposed to be in close association with polysaccharides. No mentionable amount of crystalline silica is detected by wide-angle X-ray scattering. The small-angle X-ray scattering data are consistent with the presence of colloidal, sheet-like silica agglomerates with a thickness of about 2 nm. From these results we conclude that there are at least two distinct forms of silica in E. hyemale which may have different functions. The close association of silica with cell wall polymers suggests that they may act as a polymeric template that controls the shape and size of the colloidal silica particles similar to many other biominerals and mineralised tissues. We propose that owing to its specific distribution in E. hyemale, a protective role and possibly also an important biomechanical role are among the most likely functions of silica in these plants.

The novel ER membrane protein PRO41 is essential for sexual development in the filamentous fungus Sordaria macrospora.

The filamentous fungus Sordaria macrospora develops complex fruiting bodies (perithecia) to propagate its sexual spores. Here, we present an analysis of the sterile mutant pro41 that is unable to produce mature fruiting bodies. The mutant carries a deletion of 4 kb and is complemented by the pro41 open reading frame that is contained within the region deleted in the mutant. In silico analyses predict PRO41 to be an endoplasmic reticulum (ER) membrane protein, and a PRO41-EGFP fusion protein colocalizes with ER-targeted DsRED. Furthermore, Western blot analysis shows that the PRO41-EGFP fusion protein is present in the membrane fraction. A fusion of the predicted N-terminal signal sequence of PRO41 with EGFP is secreted out of the cell, indicating that the signal sequence is functional. pro41 transcript levels are upregulated during sexual development. This increase in transcript levels was not observed in the sterile mutant pro1 that lacks a transcription factor gene. Moreover, microarray analysis of gene expression in the mutants pro1, pro41 and the pro1/41 double mutant showed that pro41 is partly epistatic to pro1. Taken together, these data show that PRO41 is a novel ER membrane protein essential for fruiting body formation in filamentous fungi.

Synthesis and characterization of SiC materials with hierarchical porosity obtained by replication techniques.

Porous silicon carbide monoliths were obtained using the infiltration of preformed SiO(2) frameworks with appropriate carbon precursors such as mesophase pitch. The initial SiO(2) monoliths possessed a hierarchical pore system, composed of an interpenetrating bicontinuous macropore structure and 13 nm mesopores confined in the macropore walls. After carbonization, further heat treatment at ca. 1,400 degrees C resulted in the formation of a SiC-SiO(2) composite, which was converted into a porous SiC monolith by post-treatment with ammonium fluoride solution. The resulting porous SiC featured high crystallinity, high chemical purity and showed a surface area of 280 m(2) g(-1) and a pore volume of 0.8 ml g(-1).