RNA Cleavage Catalyzed by Amphoteric Bis(acyl)guanidinium Derivatives

Described herein are two series (twelve compounds each) of very closely related guanidinium‐based receptors and their ability to catalyze hydrolytic cleavage of a unique RNA substrate – oligo‐dT flanked t rans‐ A ctivation R esponsive region of the HIV‐1 mRNA, TAR RNA. The significant difference in activities of otherwise very similar compounds is discussed, and direct and indirect evidences supporting our interpretation are presented. The results indicate that improvements in catalytic efficiency could be achieved with little modification of the structure of a relatively weak catalyst, and that a crucial feature could be a finely calibrated interplay between anion‐binding and proton‐donating abilities.     

Chemical mimicry: hierarchical 1D TiO2@ZrO2 core-shell structures reminiscent of sponge spicules by the synergistic effect of silicatein-α and silintaphin-1

In nature, mineralization of hard tissues occurs due to the synergistic effect of components present in the organic matrix of these tissues, with templating and catalytic effects. In Suberites domuncula, a well-studied example of the class of demosponges, silica formation is mediated and templated by an axial proteinaceous filament with silicatein-α, one of the main components. But so far, the effect of other organic constituents from the proteinaceous filament on the catalytic effect of silicatein-α has not been studied in detail. Here we describe the synthesis of core-shell TiO(2)@SiO(2) and TiO(2)@ZrO(2) nanofibers via grafting of silicatein-α onto a TiO(2) nanowire backbone followed by a coassembly of silintaphin-1 through its specifically interacting domains. We show for the first time a linker-free, one-step funtionalization of metal oxides with silicatein-α using glutamate tag. In the presence of silintaphin-1 silicatein-α facilitates the formation of a dense layer of SiO(2) or ZrO(2) on the TiO(2)@protein backbone template. The immobilization of silicatein-α onto TiO(2) probes was characterized by atomic force microscopy (AFM), optical light microscopy, and high-resolution transmission electron microscopy (HRTEM). The coassembly of silicatein-α and silintaphin-1 may contribute to biomimetic approaches that pursue a controlled formation of patterned biosilica-based biomaterials.     

Solution synthesis of nanoparticular binary transition metal antimonides

The preparation of nanoengineered materials with controlled nanostructures, for example, with an anisotropic phase segregated structure or a regular periodicity rather than with a broad range of interparticle distances, has remained a synthetic challenge for intermetallics. Artificially structured materials, including multilayers, amorphous alloys, quasicrystals, metastable crystalline alloys, or granular metals, are mostly prepared using physical gas phase procedures. We report a novel, powerful solution-mediated approach for the formation of nanoparticular binary antimonides based on presynthesized antimony nanoparticles. The transition metal antimonides M-Sb (M = Co, Ni, Cu(2), Zn) were obtained with sizes ranging from 20 and 60 nm. Through careful control of the reaction conditions, single-phase nanoparticular antimonides were synthesized. The nanophases were investigated by powder X-ray diffraction and (high resolution) electron microscopy. The approach is based on activated metal nanoparticles as precursors for the synthesis of the intermetallic compounds. X-ray powder diffraction studies of reaction intermediates allowed monitoring of the reaction kinetics. The small particle size of the reactants ensures short diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis.     

Wet chemical synthesis and a combined X-ray and Mössbauer study of the formation of FeSb2 nanoparticles

Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 M?ssbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C.     

Controlling phase formation in solids: rational synthesis of phase separated Co@Fe2O3 heteroparticles and CoFe2O4 nanoparticles

A wet chemical approach from organometallic reactants allowed the targeted synthesis of Co@Fe(2)O(3) heterodimer and CoFe(2)O(4) ferrite nanoparticles. They display magnetic properties that are useful for magnetic MRI detection.     

Quantification of surface functional groups on polymer microspheres by supramolecular host-guest interactions

We introduce a method to determine the number of accessible functional groups on a polymer microsphere surface based on the interaction between the macrocyclic host cucurbit[7]uril (CB7) and a guest reacted to the microsphere surface. After centrifugation, CB7 in the supernatant is quantified by addition of a fluorescent dye. The difference between added and detected CB7 affords the number of accessible surface functional groups.     

Theoretical reconstruction and elementwise analysis of photoelectron spectra for imidazolium-based ionic liquids

We have recently measured core level and valence band XPS, UPS, and MIES spectra of two room temperature ionic liquids composed of bis(trifluoromethylsulfonyl)imide anions ([Tf(2)N](-)) and either 1-ethyl-3-methyl-imidazolium ([EMIm](+)) or 1-octyl-3-methyl-imidazolium cations ([OMIm](+)). [T. Ikari, A. Keppler, M. Reinm?ller, W. J. D. Beenken, S. Krischok, M. Marschewski, W. Maus-Friedrichs, O. H?fft and F. Endres, e-J. Surf. Sci. Nanotechnol., 2010, 8, 241.] In the present work we analyze these spectra by means of partial density of states (pDOS) as calculated from a single ion pair of the respective ionic liquid using density functional theory (DFT). Subsequently we reconstruct the XPS and UPS spectra by considering photoemission cross sections and analyze the MIES spectra by pDOS, which provides us decisive hints to the ionic liquid surface structure.     

Tumour cell identification by means of Raman spectroscopy in combination with optical traps and microfluidic environments

Raman spectroscopy has been recognized to be a powerful tool for label-free discrimination of cells. Sampling methods are under development to utilize the unique capabilities to identify cells in body fluids such as saliva, urine or blood. The current study applied optical traps in combination with Raman spectroscopy to acquire spectra of single cells in microfluidic glass channels. Optical traps were realized by two 1070 nm single mode fibre lasers. Microflows were controlled by a syringe pump system. A novel microfluidic glass chip was designed to inject single cells, modify the flow speed, accommodate the laser fibres and sort cells after Raman based identification. Whereas the integrated microchip setup used 514 nm for excitation of Raman spectra, a quartz capillary setup excited spectra with 785 nm laser wavelength. Classification models were trained using linear discriminant analysis to differentiate erythrocytes, leukocytes, acute myeloid leukaemia cells (OCI-AML3), and breast tumour cells BT-20 and MCF-7 with accuracies that are comparable with previous Raman experiments of dried cells and fixed cells in a Petri dish. Implementation into microfluidic environments enables a high degree of automation that is required to improve the throughput of the approach for Raman activated cell sorting.