Assembly of DNA-functionalized gold nanoparticles studied by UV/Vis-spectroscopy and dynamic light scattering

The DNA mediated assembly of complementary DNA-functionalized gold nanoparticles (DNA-AuNP) was investigated by means of UV/Vis-spectroscopy and Dynamic Light Scattering (DLS). The melting temperature of the aggregates was determined to be T(m) = 31 degrees C. Characterization of the assembly at 20 degrees C, 25 degrees C and 30 degrees C showed a decrease of the initial assembly growth rate with increasing temperature. The correlation of the wavelengths at the absorbance maxima lambda(max) and the hydrodynamic radii R(h) of the AuNP assemblies proved the dependence of the optical properties on the assembly size while at higher assembly temperature (30 degrees C) a larger redshift of lambda(max) with increasing R(h) was observed than at lower temperatures. This tendency might give information about the dependence of the internal structure of the DNA-AuNP assemblies on assembly temperature. It is assumed that at higher temperatures more compact assemblies are built than at lower temperatures of 20 degrees C and 25 degrees C. To the best of our knowledge, this is the first systematic time-resolved in situ investigation of DNA-mediated AuNP assembly by UV/Vis-spectroscopy and DLS.     

Quinomethides versus unsymmetric hybrids: two variations of non-radicaloid SEM-states in four-electron redox systems of bis-4<Emphasis Type="Italic">H</Emphasis>-imidazoles

A series of bis-4H-imidazoles 1a-h has been synthesized and characterized. Due to the integration of rigid substructures, the first fluorescent 4H-imidazole 1h which possesses the substructure of pyrrolo-pyrrol was obtained. Upon protonation of bis-4H-imidazoles, a bathochromic shift of 100 to almost 200 nm was observed originating from the transformation of merocyanine chromophores into cyanines. All 4H-imidazoles were reduced chemically yielding bridged 1H-imidazoles which immediately reoxidize when exposed to air. Stable quinomethide-like species 3a,b which represent the SEM form in this four-electron redox system are only observed during the reduction of bis-4H-imidazoles 1a,b. Influenced by larger bridging elements in derivatives 1c–1h, the electronic communication between terminal 4H-imidazoles is impaired. Therefore, detection and isolation of neither quinomethide-like nor biradikaloid SEM forms succeeded. Most likely a very fast electron-transfer-step leads to unsymmetric hybrids, consisting of one 1H- and one 4H-imidazole. The new synthesized derivative 1k is not only such a stable hybrid molecule, but also may be an indication for the existence of non-quinoid SEM-forms.     

Colchicin

Colchicin was extracted from grinded seeds of meadow saffron and purified by flash chromatography and preparative HPLC. All analytical spectra were recorded and are reproduced either in the main part or in the supporting information. The NMR‐ and mass‐spectra have been interpreted and compared with theoretical calculations of the ¹³C chemical shifts. The project is a follow up of the recent book “Classics in Spectroscopy” by S. Berger und D. Sicker (Wiley‐VCH 2009).     

A New Method to Record Subglottal Pressure Waves: Potential Applications

Rapid subglottal pressure changes related to the glottal cycles influence the aerodynamics of phonation. Various methods to measure these have been developed, but are not practical for routine phoniatric use. For that reason, a noninvasive measurement tool is necessary. This article presents a technique that uses a microphone positioned at the skin of the jugular fossa to record the signal which arises in the subglottal spaces and is transmitted through the soft tissue to the surface of the skin. Using the program Glottal Segmentation of Voice and Speech, jugular microphone recordings from two healthy subjects were compared with simultaneously recorded direct intratracheal measurements during the same phonation. A systematic error arising from the transmission properties of the microphone and the soft tissue leads to phase and amplitude deviations. These must be taken into account and require correction. This correction procedure leads to high correlations and a good agreement between the two signals. Even without this correction the jugular microphone measurements proved to be useful as a diagnostic and a therapeutic tool in cases where chest resonance specific processes appear affected. In addition, they offer material for research purposes. Although based on a small number of subjects, the new method shows a good validity; testing on a larger number of subjects will probably strengthen the validity.     

Sialyl Lewisx: A “Pre‐Organized Water Oligomer”?

Organized and released: Sialyl Lewis(x) (sLe(x)) represents a "pre-organized water oligomer", that is, a surrogate for clustered water molecules attached to a scaffold. The impetus for sLe(x) binding to E-selectin is shown to be the high degree of pre-organization allowing an array of directed hydrogen bonds, and the entropic benefit of the release of water molecules from the large binding interface to bulk water (see picture).     

The role of surface defects in large organic molecule adsorption: substrate configuration effects

The role of the configuration of metal surface atoms in the interaction between individual large, planar organic molecules and a metal substrate was investigated by low-temperature scanning tunneling microscopy and density functional theory calculations, including a semi-empirical correction scheme to account for dispersion effects. As test case, we used the adsorption of the oligopyridine derivative 2-phenyl-4,6-bis(6-(pyridine-2-yl)-4-(pyridine-4-yl)pyridine-2-yl)pyrimidine (2,4'-BTP) on a stepped Ag(100) surface. Both experiment, via statistical evaluation of the adsorption site and orientation of 2,4'-BTP admolecules, and theory indicate distinct structural effects. The results are compared with the adsorption behavior of pyridine derivatives and benzene on metal surfaces. Consequences on the understanding of the interaction between heteroatoms or functional groups in large organic adsorbates and metal atoms in typical nano-scaled surface defects and hence of the interaction with more realistic metal surfaces are discussed.     

P-stereogenic trifluoromethyl derivatives of Josiphos: synthesis, coordination properties, and applications in asymmetric catalysis

Intermolecular nucleophilic substitution of a CF(3) group of bis(trifluoromethyl)phosphanes by a lithiated Ugi's amine (4) affords both diastereoisomers of the corresponding P-stereogenic trifluoromethylphosphanes 6 and 7. Separation of the isomers by column chromatography on silica gel followed by substitution of the dimethylamino group with phosphanes or pyrazoles yields the bidentate P^P (9 and 10) or P^N ligands (12 and 13) without epimerization at the stereogenic phosphorus center. The coordination properties of these bidentate ligands were investigated on the basis of crystal structures of the corresponding palladium and rhodium complexes. IR spectroscopic measurements of rhodium-carbonyl complexes 16-23 indicated the strongly electronic-withdrawing character of these phosphanes. The catalytic potential of these ligands was demonstrated in the rhodium-catalyzed hydrogenation of olefins as well as in the palladium-catalyzed allylic alkylation reaction, where high activities and enantioselectivities were observed.