Scientific publications

Treatment of diphenyl(3-thienyl)methanol HO–C(C16H13S) (1) with neodymium amide Nd[N(SiMe3)2]3 leads to Nd[OC(C16H13S)]3(thf)3} • thf (2). Single-crystal X-ray diffraction analysis of 2 reveals a mononuclear compound with an approximately octahedral geometry around the neodymium metal centre. The electrochemical investigations show that the cyclic voltammograms of 1 and 2 are only dominated by the oxidation of the thiophene moieties. Luminescence studies performed on 2 reveal the typical f-f transitions of the NdIII ion and exhibit an energy transfer from the ligand to the lanthanide ion.

Corundum (hexagonal) structure indium tin oxide (h-ITO) nanocrystals have been synthesized by subjecting an aqueous solution of In and Sn chlorides (Sn/In 8 wt.%) to a hydrothermal process followed by annealing at 450 °C in forming gas for 1 h. The annealing temperature was selected based on thermo-gravimetric analysis (TGA) and differential thermal analysis (DTA) of the dried precipitated powder, which showed a stable weight and phase at temperatures above 420 °C. X-ray diffraction (XRD) patterns showed the formation of orthorhombic InOOH precipitates that is transformed, after annealing, into h-ITO nanocrystals with 32 nm average crystal size. For nanostructure film deposition, dispersed sols of the prepared nanocrystals were spun coated on glass substrates. The films were densified by UV irradiation, whilst four-probe method was used to measure its sheet resistance. A sheet resistance as low as 10.6 kΩ □ have been reached. Scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM) showed that the films have high surface roughness and nanopores. The transmittance spectra of the nanostructure films were measured in the UV-vis-NIR wavelength range. In addition to its low resistivity, nanostructure h-ITO films showed a wide range of transparency.

Novel organoplatinum(II) complexes with 2-acetylthiophene thiosemicarbazone (ATTSC) were synthesized. The reaction of K2PtCl4 with ATTSC in 1:1 and 1:2 metal to ligand ratios yielded 1 [Pt4(ATTSC-2H)4·4DMF] and 2 [Pt(ATTSC-H)(ATTSC)Cl·3CH3OH)]. The crystal structures of these platinum chelates have been solved by single-crystal X-ray diffraction structure determinations and revealed metalation of the thiophene ring at C2 through platinum atoms. Further characterization of 1 and 2 was performed using electronic, IR, UV/vis, and NMR spectroscopies and elemental analysis. The in vitro antitumor activity of the ligand as well as 1 and 2 was determined against two different human tumor cell lines (HT-29 and HuTu-80). These tests revealed that the platinum(II) complexes are more cytotoxic than their ligand. The tetranuclear complex 1 shows higher antiproliferative activity (IC50 = 1.2 and 1.5 µM) when compared to 2 (IC50 = 3 and 5.9 µM), while the ligand has IC50 values of 8.6 and >10 µM. Compounds 1 and 2 can therefore be considered as agents with potential antitumor activity.

This Letter is in response to a recent paper by Ma et al. (CrystEngComm, 2010, 12, 750-754) which arguably studied vanadium carbide nanostructures whereas all available evidence indicates the study of vanadium oxide. We feel that it is important to communicate to the community several inconsistencies so that the interesting material reported can be seen in the right light, especially with several groups nowadays having reported similar structures from vanadium oxide synthesis.

The effect of the micro- and nanotopography on vascular cell-surface interaction is investigated using nano- and microstructured Al2O3 as model substrate. Two different nanostructured Al2O3 surfaces composed of low density (LD) and high density (HD) nanowires (NWs) were synthesized by chemical vapour deposition (CVD) and commercially available microstructured Al2O3 plates were used for comparison. A clear diverging response of human umbilical vein endothelial cells (HUVEC) and human umbilical vein smooth muscle cells (HUVSMC) was observed on these nano- and microstructured surfaces. LD Al2O3 NWs seem to enhance the proliferation of HUVECs selectively. This selective control of the cell-surface interaction by topography may represent a key issue for the future stent material design.

Using the molecular compound Zr(OBut)4 in a liquid-injection chemical vapor deposition process, microporous zirconia membranes were deposited on porous multi-layered alumina substrates consisting of a macroporous α-alumina base covered with a mesoporous γ-alumina layer. The structure of nanocrystalline zirconia (ZrO2), membranes formed by the thermal decomposition of the precursor varied depending on the decomposition temperature and the injection frequency. The deposited zirconia membranes were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and atomic force microscopy (AFM). X-ray diffraction analysis patterns of the deposits obtained at 500 and 600 °C indicated a mixture of tetragonal and monoclinic ZrO2 phases, whereas the fraction of the monoclinic phase increased at higher substrate temperature and injection frequency. Morphology and surface roughness are strongly dependent on the process parameters. ZrO2 membranes prepared by the liquid-injection chemical vapor deposition had a microporous structure with less than 1 nm Kelvin diameter. The liquid-injection chemical vapor deposition is a unique method to prepare microporous membranes in one step without any post-treatment.

In this paper, we expressed murine gap junction protein Cx43 in Dictyostelium discoideum by introducing the specific vector pDXA. In the first step, the successful expression of Cx43 and Cx43-eGFP was verified by (a) Western blot (anti-Cx43, anti-GFP), (b) fluorescence microscopy (eGFP-Cx43 co-expression, Cx43 immunostaining), and (c) flow cytometry analysis (eGFP-Cx43 co-expression). Although the fluorescence signals from cells expressing Cx43-eGFP detected by fluorescence microscopy seem relatively low, analysis by flow cytometry demonstrated that more than 60% of cells expressed Cx43-eGFP. In order to evaluate the function of expressed Cx43 in D. discoideum, we examined the hemi-channel function of Cx43. In this series of experiments, the passive uptake of carboxyfluorescein was monitored using flow cytometric analysis. A significant number of the transfected cells showed a prominent dye uptake in the absence of Ca2+. The dye uptake by transfected cells in the presence of Ca2+ was even lower than the non-specific dye uptake by non-transformed Ax3 orf+ cells, confirming that Cx43 expressed in D. discoideum retains its Ca2+-dependent, specific gating function. The expression of gap junction proteins expressed in slime molds opens a possibility to the biological significance of intercellular communications in development and maintenance of multicellular organisms.

Nanoscaled ZnO was synthesized by an electrochemical process using zinc or Al-alloyed zinc electrodes in an aqueous system with acetic acid as a conductive salt. Depending on the synthetical parameters, the precipitated precursor solids were found to consist of various compounds such as zincite, presumably δ-Zn(OH)2, β1-Zn(OH)2, ε-Zn(OH)2, Zn5(CO3)2(OH)6 and, in case an Al-alloyed electrode was used for the synthesis, Zn0.71Al0.29(OH)2(CO3)0.145·xH2O. The intermediate solids served as precursors for the subsequent thermal treatment resulting in zincite powders with various morphologies. Depending on the processing conditions, zincite was formed between 100 and 260 °C with a mean crystallite size between 6 and 25 nm. Selected zincite powders were pressed to pellets, sintered at temperatures between 900 and 1,100 °C and characterized by measurements of the electrical bulk conductivities, yielding values up to 1.69 S cm−1 in samples with 1.24 wt% Al. Comparison with samples prepared by precipitation methods showed that the latter had values of up to 44 S cm−1.

We analyzed the contact mechanisms of bioinspired microfibrillar adhesives using in situ scanning electron microscopy. During adhesion tests we observed that (i) the superior adhesion of mushroom-shaped fibrils is assisted by the stochastic nature of detachment, (ii) the aspect ratio of microfibrils influences the bending/buckling behavior and the contact reformation, and (iii) the backing layer deformation causes the microfibrils to elastically interact with each other. These studies give new insights into the mechanisms responsible for adhesion of bioinspired fibrillar adhesives.

The size effect in body-centered cubic metals is comprehensively investigated through micro/nano-compression tests performed on focused ion beam machined tungsten (W), molybdenum (Mo) and niobium (Nb) pillars, with single slip [2 3 5] and multiple slip [0 0 1] orientations. The results demonstrate that the stress-strain response is unaffected by the number of activated slip systems, indicating that dislocation-dislocation interaction is not a dominant mechanism for the observed diameter dependent yield strength and strain hardening. Furthermore, the limited mobility of screw dislocations, which is different for each material at ambient temperature, acts as an additional strengthening mechanism leading to a material dependent size effect. Nominal values and diameter dependence of the flow stress significantly deviate from studies on face-centered cubic metals. This is demonstrated by the correlation of size dependence with the material specific critical temperature. Activation volumes were found to decrease with decreasing pillar diameter further indicating that the influence of the screw dislocations decreases with smaller pillar diameter.