Cyclic and acyclic sulfonimides in reactions with Rh(II)-ketocarbenoids: a new access to chemoselective O-functionalization of the imidic carbonyl groups

Catalytic decomposition of diazoacetylacetone, diazoacetoacetic, diazomalonic, and diazoacetic esters using dirhodium tetraacetate in the presence of isothiazol-3(2H)-one 1,1-dioxides and a number of N-(arenesulfonyl)carboxamides in solutions of methylene chloride or dichloroethane gives rise to O-alkylation of the imidic carbonyl groups by Rh(II)-carbenoids and the formation of O-alkylimidates as the final products. The reaction proceeds with high chemoselectivity via carbonyl ylides and offers a powerful method for the synthesis in good yields of the imidates with polyfunctional O-alkyl groups. On the basis of X-ray analysis and 1H- and 13C-NMR studies it was shown that the resulting acyclic O-alkylimidates have the E-configuration in the solid state and in solution. Unlike acyclic analogues, the cyclic carbonyl ylide derived from substituted diazosaccharin by intramolecular cyclization of the appropriate diketocarbenoid is capable of reacting with DMAD in a 1,3-cycloaddition process.     

A novel X‐ray diffractometer for studies of liquid–liquid interfaces

The study of liquid–liquid interfaces with X‐ray scattering methods requires special instrumental considerations. A dedicated liquid surface diffractometer employing a tilting double‐crystal monochromator in Bragg geometry has been designed. This diffractometer allows reflectivity and grazing‐incidence scattering measurements of an immobile mechanically completely decoupled liquid sample, providing high mechanical stability. The available energy range is from 6.4 to 29.4 keV, covering many important absorption edges. The instrument provides access in momentum space out to 2.54 Å^?1 in the surface normal and out to 14.8 Å^?1 in the in‐plane direction at 29.4 keV. Owing to its modular design the diffractometer is also suitable for heavy apparatus such as vacuum chambers. The instrument performance is described and examples of X‐ray reflectivity studies performed under in situ electrochemical control and on biochemical model systems are given.     

Stably embedded minimal hypersurfaces

We use Schoen’s curvature estimates to prove that the subfocal tubular neighborhood of a nonplanar minimal hypersurface with bounded second fundamental form, stably embedded in whose radius decays sufficiently slowly cannot be embedded. In particular such hypersurfaces admit no embedded tubular neighborhoods of constant radius, whatever small the radius. However, assuming a further hypothesis on the embedding, we prove that such hypersurfaces admit an embedded tube whose radius decays sufficiently fast.      

Fermionization of two distinguishable fermions

We study a system of two distinguishable fermions in a 1D harmonic potential. This system has the exceptional property that there is an analytic solution for arbitrary values of the interparticle interaction. We tune the interaction strength and compare the measured properties of the system to the theoretical prediction. For diverging interaction strength, the energy and square modulus of the wave function for two distinguishable particles are the same as for a system of two noninteracting identical fermions. This is referred to as fermionization. We have observed this phenomenon by directly comparing two distinguishable fermions with diverging interaction strength with two identical fermions in the same potential. We observe good agreement between experiment and theory. By adding more particles our system can be used as a quantum simulator for more complex systems where no theoretical solution is available.     

Atmospheric pressure laser desorption/ionization on porous silicon

A recently developed commercial atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) source (MassTech, Inc.) was modified to adopt commercially available DIOS plates (Mass Consortium Corp.) for the studies of laser desorption from the surface of porous silicon under atmospheric pressure conditions. The feasibility of atmospheric pressure laser desorption/ionization from the surface of porous silicon (AP-DIOS) was demonstrated. The advantages of this new AP-DIOS technique include reasonably good sensitivity (subpicomole range for standard peptide mixtures), simplicity of sample preparation, uniformity of target spots and the absence of matrix peaks in the spectra. The AP-DIOS source was interfaced with a commercial ion trap (LCQ Classic, Thermo Finnigan) which additionally provides a unique MS(n) capability. The AP-DIOS spectrum of 250 fmol of unseparated tryptic digest of bovine serum albumin (BSA) was compared with that of AP-MALDI for the same compound. AP-DIOS offers significantly better coverage for the digest components in the mass range 200-1000 Da. The combined data of both techniques enabled us to nearly double the number of matched peaks in BSA digest analysis compared with AP-DIOS or AP-MALDI analysis separately.     

Hypersurfaces with {H_{r+1}} = 0 in {\mathbb{H}^n \times \mathbb{R}}

We prove the existence of rotational hypersurfaces in \({\mathbb{H}^n \times \mathbb{R}}\) with \({H_{r+1} = 0}\) (r-minimal hupersurfaces) and we classify them. Then we prove some uniqueness theorems for r-minimal hypersurfaces with a given (finite or asymptotic) boundary. In particular, we obtain a Schoen-type theorem for two ended complete hypersurfaces.     

Evidence for C-C bond cleavage by H2O2 in a mesoporous CMK-5 type carbon at room temperature

We reported an evidence for C-C bond cleavage by milder oxidizing agent H2O2 in a mesoporous CMK-5 type carbon at room temperature.