Synthesis and Characterization of Three Homoleptic Bismuth Silanolates: [Bi(OSiR3)3] (R = Me,Et, iPr)

The bismuth tris(triorganosilanolates) [Bi(OSiR₃)₃] ( 1 , R = Me; 2 , R = Et; 3 , R = iPr) were prepared by reaction of R₃SiOH with [Bi(OtBu)₃]. Compound 1 crystallizes in the triclinic space group with Z = 2 and the lattice constants a = 10.323(1) Å, b = 13.805(1) Å, c = 21.096(1) Å and α = 91.871(4)°, β = 94.639(3)°, γ = 110.802(3)°. In the solid state compound 1 is a trimer as result of weak intermolecular bismuth‐oxygen interactions with Bi–O distances in the range 2.686(6)–3.227(3) Å. The coordination at the bismuth atoms Bi(1) and Bi(3) is best described as 3 + 2 coordination whereas Bi(2) shows a 3 + 3 coordination. The intramolecular Bi–O distances fall in the range 2.041(3)–2.119(3) Å. Compound 3 crystallizes in the orthorhombic space group Pbcm with Z = 4 and the lattice constants a = 7.201(1) Å, b = 23.367(5) Å and c = 20.893(1) Å, whereas the triethylsilyl‐derivative 2 is liquid. In contrast to [Bi(OSiMe₃)₃] ( 1 ) compound 3 is monomeric in the solid state, but shows similar intramolecular Bi–O distances in the range 1.998(2)–2.065(5) Å. The bismuth silanolates are highly soluble in common organic solvents and strongly moisture sensitive. Compound 1 shows the lowest thermal stability.     

Monitoring the heterogeneity in single cell responses to drugs using electrochemical impedance and electrochemical noise

Impedance spectroscopy is a widely used technique for monitoring cell–surface interactions and morphological changes, typically based on averaged signals from thousands of cells. However, acquiring impedance data at the single cell level, can potentially reveal cell-to-cell heterogeneity for example in response to chemotherapeutic agents such as doxorubicin. Here, we present a generic platform where light is used to define and localize the electroactive area, thus enabling the impedance measurements for selected single cells. We firstly tested the platform to assess phenotypic changes in breast cancer cells, at the single cell level, using the change in the cell impedance. We next show that changes in electrochemical noise reflects instantaneous responses of the cells to drugs, prior to any phenotypical changes. We used doxorubicin and monensin as model drugs and found that both drug influx and efflux events affect the impedance noise signals. Finally, we show how the electrochemical noise signal can be combined with fluorescence microscopy, to show that the noise provides information on cell susceptibility and resistance to drugs at the single cell level. Together the combination of electrochemical impedance and electrochemical noise with fluorescence microscopy provides a unique approach to understanding the heterogeneity in the response of single cells to stimuli where there is not phenotypic change.

A light addressable single-cell impedance technique for cell adhesion monitoring and measurement of a cell''s drug response based on electrochemical noise is introduced.     

Fette

Ohne Zusammenfassung     

From {Bi22O26} to chiral ligand-protected {Bi38O45}-based bismuth oxido clusters

The reaction of [Bi(22)O(26)(OSiMe(2)tBu)(14)] (1) in THF with salicylic acid gave [Bi(22)O(24)(HSal)(14)] (2) first, which was converted into [Bi(38)O(45)(HSal)(22)(OH)(2)(DMSO)(16.5)]·DMSO·H(2)O (3·DMSO·H(2)O) after dissolution and crystallization from DMSO. Single-crystal X-ray diffraction analysis and ESI mass spectrometry associated with infrared multi-photon dissociation (IRMPD) tandem MS experiments confirm the formation of the large and quite stable bismuth oxido cluster 3. The reaction of compound 2 with the butoxycarbonyl(BOC)-protected amino acids phenylalanine and valine (BOC-PheOH and BOC-ValOH), respectively, resulted in the formation of chiral [Bi(38)O(45)(BOC-AA)(22)(OH)(2)] (AA=deprotonated amino acid), as shown by a combination of different analytical techniques such as elemental analysis, dynamic light scattering, circular dichroism spectroscopy, and ESI mass spectrometry.     

Reconstructive acoustic thermotomography of biological objects

An algebraic reconstructive tomography algorithm for mapping the internal temperature field in q section of a biological object is adapted for use in a multichannel scanning acoustic thermotomograph. For some types of thermodynamic temperature distribution, using the computer simulation method, the distributions of the acoustic brightness temperature are obtained allowing for the antenna system geometry and damping in the biological medium. Institute of Applied Physics, Russian Academy of Sciences, Nizhny Novgorod, Russia. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 40, No. 6, pp. 752–760, June, 1997.     

Ein vollautomatisch arbeitendes Torsionspendel für den Temperaturbereich von −180°C bis + 250°C

Zusammenfassung Zur Ermittlung des komplexen SchubmodulsG ^* bei Kunststoffen wurde ein Torsionspendel an einen Prozeßrechner angeschlossen. Das Meßsystem gestattet es, Messungen in einem Temperaturbereich von –180°C bis +250°C bei einer konstanten Schwingungsfrequenz von 1 Hz ± 0,09 Hz vollautomatisch durchzuführen. Der Rechner hat die Aufgabe, das Experiment zu steuern, die Versuchsbedingungen zu kontrollieren, die Meßwerte zu erfassen und die Auswertung durchzuführen. Die Ergebnisse können in Form von Tabellen oder graphisch ausgegeben werden. Ferner ist es möglich, die Ergebnisse auf dem Massenspeicher des Rechners in einer Datei abzulegen.

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Summary A torsional pendulum has been connected to a minicomputer in order to measure the complex shear modulus (G ^*). This experimental set-up allows to take computer controlled measurements in the temperaturerange –180°C to +250°C at a constant oscillation frequency of 1 Hz ± 0,09 Hz. The setting and controlling of the experimental parameters, the take-up of the data and the calculations are performed by the computer. The results are obtained in tabulated form or in form of plotted diagrams. In addition it is possible to store the results on the disc of the computer.

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Mit 10 Abbildungen     

Poly(2‐vinyl pyridine)‐block‐Poly(ethylene oxide) Featuring a Furan Group at the Block Junction—Synthesis and Functionalization

Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross‐linkable nanostructured materials via Diels–Alder reactions. Here, the use of FGE for the mid‐chain functionalization of a P2VP‐b‐PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP₆₈‐FGE‐b‐PEO₃₉₀, which can be subsequently addressed in Diels–Alder reactions using maleimide‐functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero‐grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP₆₈‐FGE‐b‐PEO₃₉₀, a powerful tool for selective functionalization reactions, including the modification of surfaces.

     

Application of129Xe NMR to polymer blends

¹²⁹Xe NMR experiments on two different polymer blends are described. The first system, a blend of polypropylene (PP) and the copolymer of polypropylene and polyethylene (EP), shows separate domains of polypropylene and of the copolymer. The latter phase forms rubbery domains in the polypropylene matrix. The second system is the compatible blend of polyvinylidenefluoride and polymethylmethacrylate. For the incompatible blend two Xe resonances are found, one for Xe absorbed in the matrix and one for Xe in the rubbery EP phase. The chemical shift of the Xe absorbed in the rubbery phase can be related to the polyethylene content of the copolymer. The line widths and chemical shifts are affected by the polymer motions as a function of the temperature. Although the system has two very different glass transition temperatures, it is striking to see that upon approaching the polypropylene glass transition temperature the Xe resonance of Xe in the rubbery phase is also affected. Due to the dipolar interaction between Xe spins and polymer proton spins, cross-polarization experiments can be performed. This allows the measurement of correlated NMR spectra. The compatible blend shows only one line with a chemical shift proportional to the composition.     

A Tetrameric Neodymium Silanolate: [Nd(OSiMe3)3]4

The title compound [Nd(OSiMe₃)₃]₄ ( 1 ) was prepared by reaction of [Nd{N(SiMe₃)₂}₃] with Me₃SiOH in toluene at room temperature. Compound 1 crystallized from a concentrated toluene solution in the monoclinic space group P2₁/n with the lattice constants a = 15.144(1) Å, b = 25.142(1) Å, c = 20.391(1) Å and β = 103.755(2)°. In the solid state a tetramer is observed which shows Nd‐O bond distances in the range 2.129(2)‐2.675(2) Å.     

Untersuchung von Butter

Ohne Zusammenfassung