Perfluorodecalin-soluble fluorescent dyes for the monitoring of circulating nanocapsules with intravital fluorescence microscopy.

Perfluorodecalin (PFD) is an established artificial oxygen carrier due to its physical capability to solve the respiratory gases oxygen and carbon dioxide. PFD-filled poly(n-butyl-cyanoacrylate) (PACA) nanocapsules are already discussed as effective artificial oxygen carriers, and their principal suitability for intravenous administration had been shown. To further elucidate their action in vivo, it is imperative to characterise their preclinical safety and particularly their biodistribution. For these purposes, intravital fluorescence microscopy would display an attractive technique in order to monitor the PACA nanocapsules in vivo, but unfortunately, it is impossible to stain the PACA nanocapsules with a fluorescent dye fulfilling special criteria required for in vivo microscopy. In order to develop such a dye, a long-chained fluorinated thiol was used to modify a BODIPY derivative that is a highly fluorescent organic compound belonging to the difluoro-boraindacene family, as well as to functionalise mesoscopic systems, such as CdSe/ZnS-quantum dots and gold nanoparticles. Furthermore, a functionalisation of porphyrin derivatives was investigated by placing divalent ions in the centre of these systems. Due to the high solubility of all synthesised dyes in PFD, it should be possible to stain PFD-filled particles in general. However, only the functionalised BODIPY derivative was suitable for in vivo monitoring of the PFD-filled PACA nanocapsules.

A dynamic model of nutrient uptake by root hairs.

Root hairs are known to be important in the uptake of sparingly soluble nutrients by plants, but quantitative understanding of their role in this is weak. This limits, for example, the breeding of more nutrient-efficient crop genotypes. We developed a mathematical model of nutrient transport and uptake in the root hair zone of single roots growing in soil or solution culture. Accounting for root hair geometry explicitly, we derived effective equations for the cumulative effect of root hair surfaces on uptake using the method of homogenization. Analysis of the model shows that, depending on the morphological and physiological properties of the root hairs, one of three different effective models applies. They describe situations where: (1) a concentration gradient dynamically develops within the root hair zone; (2) the effect of root hair uptake is negligibly small; or (3) phosphate in the root hair zone is taken up instantaneously. Furthermore, we show that the influence of root hairs on rates of phosphate uptake is one order of magnitude greater in soil than solution culture. The model provides a basis for quantifying the importance of root hair morphological and physiological properties in overall uptake, in order to design and interpret experiments in different circumstances.

Growth model for arbuscular mycorrhizal fungi.

In order to quantify the contribution of arbuscular mycorrhizal (AM) fungi to plant phosphorus nutrition, the development and extent of the external fungal mycelium and its nutrient uptake capacity are of particular importance. We develop and analyse a model of the growth of AM fungi associated with plant roots, suitable for describing mechanistically the effects of the fungi on solute uptake by plants. The model describes the development and distribution of the fungal mycelium in soil in terms of the creation and death of hyphae, tip-tip and tip-hypha anastomosis, and the nature of the root-fungus interface. It is calibrated and corroborated using published experimental data for hyphal length densities at different distances away from root surfaces. A good agreement between measured and simulated values was found for three fungal species with different morphologies: Scutellospora calospora (Nicol. & Gerd.) Walker & Sanders; Glomus sp.; and Acaulospora laevis Gerdemann & Trappe associated with Trifolium subterraneum L. The model and findings are expected to contribute to the quantification of the role of AM fungi in plant mineral nutrition and the interpretation of different foraging strategies among fungal species.

{Ge9[Si(SiMe3)3]2}(2-): a starting point for mixed substituted metalloid germanium clusters.

Deeper investigations on the silylation reaction of the Ge9(4-) Zintl anion are provided. The reaction of K4Ge9 with two equivalents of ClHyp (Hyp = Si(SiMe3)3) gives the metalloid cluster compound [Ge9(Hyp)2](2-). Subsequent reactions with this compound give access to the first mixed trisubstituted metalloid cluster [Ge9(Hyp)2(Hyp(Ph3))](-) (Hyp(Ph3) = Si(SiMe3)2(SiPh3)), opening a way to a variety of mixed substituted Ge9 clusters for future investigations.

L-System model for the growth of arbuscular mycorrhizal fungi, both within and outside of their host roots.

Development of arbuscular mycorrhizal fungal colonization of roots and the surrounding soil is the central process of mycorrhizal symbiosis, important for ecosystem functioning and commercial inoculum applications. To improve mechanistic understanding of this highly spatially and temporarily dynamic process, we developed a three-dimensional model taking into account growth of the roots and hyphae. It is for the first time that infection within the root system is simulated dynamically and in a spatially resolved way. Comparison between data measured in a calibration experiment and simulated results showed a good fit. Our simulations showed that the position of the fungal inoculum affects the sensitivity of hyphal growth parameters. Variation in speed of secondary infection and hyphal lifetime had a different effect on root infection and hyphal length, respectively, depending on whether the inoculum was concentrated or dispersed. For other parameters (branching rate, distance between entry points), the relative effect was the same independent of inoculum placement. The model also indicated that maximum root colonization levels well below 100%, often observed experimentally, may be a result of differential spread of roots and hyphae, besides intrinsic plant control, particularly upon localized placement of inoculum and slow secondary infection.

UV photoexcitation of a dissolved metalloid Ge9 cluster compound and its extensive ultrafast response.

Femtosecond pump-probe absorption spectroscopy in tetrahydrofuran solution has been used to investigate the dynamics of a metalloid cluster compound {Ge9[Si(SiMe3)3]3}(-). Upon UV photoexcitation, the transients in the near-infrared spectral region showed signatures reminiscent of excess electrons in THF (bound or quasi-free) whereas in the visible part excited state dynamics of the cluster complex dominates.

Ga(22)

A metal-rich intermediate was captured prior to metal formation by means of a substitution reaction during the disproportionation of a metastable Ga(I) bromide solution. In the thus obtained Ga(22) cluster (see structure), the central gallium atom displays the unusual coordination number of 13.

Si(SiMe3)2SiPh3 - a ligand for novel sub-valent tin cluster compounds.

For the synthesis of metalloid tin cluster compounds applying the disproportionation reaction of a Sn(i) halide, silyl ligands, especially the symmetric Si(SiMe3)3 has proven to be extremely useful. Silyl ligands of lower symmetry where e.g. one SiMe3 group is substituted with SiPh3 are thereby unexplored, although the synthesis of the anionic silyl precursors is quite easy, referring to previously described methods. Here the synthesis of the silanide [Si(SiMe3)2(SiPh3)](-) as its potassium () as well as its lithium salt () in excellent yield is presented. proved to be a suitable starting material for the synthesis of subvalent tin compounds as shown by the reaction with tin halides in oxidation state +2 (SnCl2) and +1 (SnCl); i.e. on the one hand the anticipated stannide [Sn(Si(SiMe3)2SiPh3)2Cl](-) could be isolated and on the other hand the unexpectedly partly substituted ring compound Cl4Sn4[Si(SiMe3)2SiPh3]4 is obtained. As no elemental tin is formed during the reaction with SnCl, metalloid tin clusters may be present in solution too, which is supported by the nearly black color of the reaction mixture, showing that might be a suitable ligand for the synthesis of such cluster compounds.

Superconductivity in a molecular metal cluster compound.

Compelling evidence for band-type conductivity and even bulk superconductivity below Tc approximately 8 K has been found in (69,71)Ga NMR experiments in crystalline ordered, giant Ga84 cluster compounds. This material appears to represent the first realization of a theoretical model proposed by Friedel in 1992 for superconductivity in ordered arrays of weakly coupled, identical metal nanoparticles.

Muon spin relaxation studies of superconductivity in a crystalline array of weakly coupled metal nanoparticles.

We report muon-spin-relaxation studies in weak transverse fields of the superconductivity in the metal cluster compound, Ga84[N(SiMe3)2]20-Li6Br2(thf)20.2 toluene. The temperature and field dependence of the muon-spin-relaxation rate and Knight shift clearly evidence type II bulk superconductivity below Tc approximately 7.8 K, with Bc1 approximately 0.06 T, Bc2 approximately 0.26 T, kappa approximately 2, and weak flux pinning. The data are well described by the s-wave BCS model with weak electron-phonon coupling in the clean limit. A qualitative explanation for the conduction mechanism in this novel type of narrow-band superconductor is presented.

[Ga18(SitBu3)8] and [Ga22(SitBu3)8]--syntheses and structural characterization of novel gallium cluster compounds.

The novel neutral gallium cluster compounds [Ga18R*8] (1) and [Ga22R*8] (2) are obtained by warming up a metastable solution of gallium(I) bromide in THF/C6H5CH3 after addition of equimolar amounts of supersilyl sodium NaR* from -78 degrees C to room temperature (R* = SitBu3 = supersilyl). From X-ray structure analyses, the observed arrangements of the 18 and 22 Ga atoms in 1 and 2, respectively, are comparable with an 18 atom section of the beta-Ga modification, or show at least some kind of relationship to a 22 atom section of the Ga-III modification. This allows a description of both the clusters as metalloid. The topology of the atoms in 2 is also well explained by the Wade-Mingos rules as an eightfold capped closo-Ga14 cluster, whereby the Ga atoms of Ga14 occupy the center and the corners of a cuboctahedron with one Ga3 face replaced by a Ga4 face. Some concepts are presented about the formation mechanism, the cluster growth, and the metalloid character of the two Ga cluster compounds.