Origin and Use of Hydroxyl Group Tolerance in Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Catalysts

The origin of hydroxyl group tolerance in neutral and especially cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes has been investigated. A wide range of catalysts was prepared and tested. Most cationic complexes can be handled in air without difficulty and display an unprecedented stability towards water and alcohols. NHC complexes were successfully used with substrates containing the hydroxyl functionality in acyclic diene metathesis polymerization, homo-, cross and ring-opening cross metathesis reactions. The catalysts remain active even in 2-PrOH and are applicable in ring-opening metathesis polymerization and alkene homometathesis using alcohols as solvent. The use of weakly basic bidentate, hemilabile anionic ligands such as triflate or pentafluorobenzoate and weakly basic aromatic imido ligands in combination with a sterically demanding 1,3-dimesitylimidazol-2-ylidene NHC ligand was found essential for reactive and yet robust catalysts.     

The Diversity of a Polyclonal FluCell-SELEX Library Outperforms Individual Aptamers as Emerging Diagnostic Tools for the Identification of Carbapenem Resistant Pseudomonas aeruginosa

Textbook procedures require the use of individual aptamers enriched in SELEX libraries which are subsequently chemically synthesized after their biochemical characterization. Here we show that this reduction of the available sequence space of large libraries and thus the diversity of binding molecules reduces the labelling efficiency and fidelity of selected single aptamers towards different strains of the human pathogen Pseudomonas aeruginosa compared to a polyclonal aptamer library enriched by a whole-cell-SELEX involving fluorescent aptamers. The library outperformed single aptamers in reliable and specific targeting of different clinically relevant strains, allowed to inhibit virulence associated cellular functions and identification of bound cell surface targets by aptamer based affinity purification and mass spectrometry. The stunning ease of this FluCell-SELEX and the convincing performance of the P. aeruginosa specific library may pave the way towards generally new and efficient diagnostic techniques based on polyclonal aptamer libraries not only in clinical microbiology.     

An Unexpected Transannular [4+2] Cycloaddition during the Total Synthesis of (+)‐Norcembrene 5

We report a concise and versatile total synthesis of the diterpenoid (+)‐norcembrene 5 from simple building blocks. Ring‐closing metathesis and an auxiliary‐directed 1,4‐addition are the key steps of our synthetic route. During the synthesis, an unprecedented, highly oxidized pentacyclic structural motif was established from a furanocembranoid through transannular [4+2] cycloaddition.     

An example of an SL2-Hilbert scheme with multiplicities

In [AB05], Alexeev and Brion have introduced the notion of invariant Hilbert schemes. We determine the invariant Hilbert scheme of the zero fibre of the moment map of an action of SL₂ on ( \mathbbC² ) ^?6 {\left( {{\mathbb{C}^2}} \right)^{ \oplus 6}} as one of the first examples of invariant Hilbert schemes with multiplicities. While doing this, we present a general procedure for realizing these calculations. We also consider questions of smoothness and connectedness and thereby show that our Hilbert scheme gives a resolution of singularities of the symplectic reduction of the action.     

Antibunching in the emission of a single tetrachromophoric dendritic system

The photophysics of a dendrimer containing four chromophores are investigated at the single-molecule level. First, the multichromophoric character of single dendrimers' absorption is probed by modulating the linear polarization of the excitation beam. Subsequently, using circular polarization, the same dendrimers are excited, and their fluorescence transients are recorded. Using pulsed excitation in combination with the classical Hanbury-Brown and Twiss coincidence setup the presented data demonstrate that efficient singlet-singlet annihilation ensures that always only one photon is emitted even when several excitations are generated in an individual multichromophoric molecule.     

Viscoelastic shear properties of in vivo breast lesions measured by MR elastography

Elastography is a technique to assess the viscoelastic properties of tissue by measuring an acoustic wave propagating though the object. Here, the technique is applied in the course of standard MR mammography to 15 patients with different pathologies (six breast cancer cases, six fibroadenoma cases and three mastopathy cases). Low-frequency mechanical waves are coupled longitudinally into the tissue in order to obtain sufficient wave amplitude throughout the entire breast. This leads to the presence of a substantial fraction of compressional waves, which contribute to the total displacement field. It is shown theoretically that the correct evaluation of these contributions from the compressional wave is rather difficult due to the almost incompressible nature of tissue. To overcome this problem, it is proposed to apply the curl-operator to the measured displacement field in order to completely remove contributions from the compressional wave. Results from simulations and a breast phantom demonstrate the feasibility of the technique. The in vivo results show a good separation between breast cancer and benign fibroadenoma utilizing the shear modulus. Breast cancer appears on average 2.2 (P<.001) times stiffer. All breast cancer cases showed a good delineation to the surrounding breast tissue with an average elevation of a factor of 3.3 (P< 1.4 x 10(-6)). The results as obtained for the shear viscosity do not indicate to be useful for separating benign from malignant lesions.     

Self-poisoning of crystal nuclei in hard-rod liquids

We report a Monte Carlo study of the pathway for crystal nucleation in a fluid of hard, colloidal rods. In the earliest stages of nucleation, a lamellar crystallite forms. Subsequent thickening of this lamella is hampered by the fact that the top and bottom surfaces of this crystallite are preferentially covered by rods that align parallel to the surface. As a consequence, subsequent growth of individual crystals is stunted. Experimental evidence for such stunted crystal growth has recently been reported by Maeda and Maeda in experiments on suspensions of colloidal rods [Phys. Rev. Lett. 90, 018303 (2003)]]. The simulations suggest that, in experiments, the growth of multilayer colloidal crystals can be selectively enhanced by the application of an external aligning field.     

2-Acetamino-1,2-dideoxynojirimycin—lysine hybrids as hexosaminidase inhibitors

Cyclisation by double reductive amination of 2-acetamino-2-deoxy-d-xylo-hexos-5-ulose with N-2 protected l-lysine derivatives provided 2-acetamino-1,2-dideoxynojirimycin derivatives without any observable epimer formation at C-5. Modifications on the lysine moiety gave access to lipophilic derivatives that exhibited improved hexosaminidase inhibitory activities.