New heterocycles with cycloamidine substructure and their ringtransformation reactions with acetylene dicarboxylic ester

The synthesis of pyrido[2,1‐c]‐1,2,4‐triazines 6 , pyrido[1,2‐b]‐1,2,4‐triazines 7 and pyrido[1,2‐b]pyri‐dazines 8 respectively by cycloacylation of derivatives of pyridine with imidoylchlorides of type 2 is described. The heterocycles of type 6 as well as of type 7 can be ring‐transformed with dimethyl acetylenedicarboxylate. In contrast to pyrido[1,2‐a]pyrazines 1, a complex reaction including cleavage of the acetylene subunit takes place. Starting from compound 6a , the pyrrolo[2,3‐d]imidazole 11a could be isolated from a mixture of unidentified by‐products, whereas derivatives 7 gave nearly quantitatively the tricyclic products of type 12 .     

Targeted next-generation sequencing by specific capture of multiple genomic loci using low-volume microfluidic DNA arrays

We report a flexible method for selective capture of sequence fragments from complex, eukaryotic genome libraries for next-generation sequencing based on hybridization to DNA microarrays. Using microfluidic array architecture and integrated hardware, the process is amenable to complete automation and does not introduce amplification steps into the standard library preparation workflow, thereby avoiding bias of sequence distribution and fragment lengths. We captured a discontiguous human genomic target region of 185 kb using a tiling design with 50mer probes. Analysis by high-throughput sequencing using an Illumina/Solexa 1G Genome Analyzer revealed 2150-fold enrichment with mean per base coverage between 4.6 and 107.5-fold for the individual target regions. This method represents a flexible and cost-effective approach for large-scale resequencing of complex genomes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Stephan Bau and Nadine Schracke contributed equally to this work.     

Atmospheric control of gel-oxide transformation in sol–gel derived Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> fibers

Via sol–gel processing metal–organic fibers were produced and dried up to 140 °C. For these gel fibers the influence of a treatment in different atmospheres was investigated for the temperature range of 200–850 °C. The atmospheres were nitrogen, water vapor, evaporated nitric and hydrochloric acid and evaporated hydrogen peroxide. In the presence of moisture and especially with acidic moisture fibers were transformed almost completely to their oxide composition (82 mol% Al₂O₃·18 mol% Y₂O₃). In these inorganic amorphous structures considerable differences were observed on several structural levels. On the atomic scale, the coordination of Al ions was investigated by ²⁷Al MAS NMR and skeletal density by He-pycnometry. Porosity in the nm scale was characterized by N₂-sorption. As a macroscopic effect of different treatment atmospheres, the longitudinal shrinkage was observed. For fibers treated at 500 °C the relative shrinkage varied by 100% (comparing water vapor and nitrogen atmosphere). No simple correlation between the release of organic constituents, the formation of porosity and the shrinkage could be found. These aspects were controlled by the rigidity of the inorganic network against atomic reconstitution. The kind of atmosphere was found to be an effective parameter to control various aspects of the xerogel structure.     

‐bounded ‐calculus for sectorial operators via generalized Gaussian estimates

We show that, for negative generators of analytic semigroups, a bounded ‐calculus self‐improves to an ‐bounded ‐calculus in an appropriate scale of ‐spaces if the semigroup satisfies suitable generalized Gaussian estimates. As application of our result we obtain that large classes of differential operators have an ‐bounded ‐calculus.     

Protein-Templated Hit Identification through an Ugi Four-Component Reaction**

Kinetic target-guided synthesis represents an efficient hit-identification strategy, in which the protein assembles its own inhibitors from a pool of complementary building blocks via an irreversible reaction. Herein, we pioneered an in situ Ugi reaction for the identification of novel inhibitors of a model enzyme and binders for an important drug target, namely, the aspartic protease endothiapepsin and the bacterial β-sliding clamp DnaN, respectively. Highly sensitive mass-spectrometry methods enabled monitoring of the protein-templated reaction of four complementary reaction partners, which occurred in a background-free manner for endothiapepsin or with a clear amplification of two binders in the presence of DnaN. The Ugi products we identified show low micromolar activity on endothiapepsin or moderate affinity for the β-sliding clamp. We succeeded in expanding the portfolio of chemical reactions and biological targets and demonstrated the efficiency and sensitivity of this approach, which can find application on any drug target.     

The Subbromide Bi5Br4 – On the Existence of a Hidden Phase

Black and irregularly shaped crystals of the bismuth-rich bromide Bi₅Br₄ were obtained as a by-product of the reaction of CsBr, Bi, and BiBr₃. X-ray diffraction on a single-crystal revealed its orthorhombic structure with the space group Pmmn (no. 59) and lattice parameters a = 1800.0(2) pm, b = 1476.1(1) pm, and c = 924.5(2) pm at 296 K. The structure is composed of Bi₈²⁺ and Bi₉⁵⁺ polycations and bromidobismuthate(III) anions according to the structured formula Bi₅Br₄ = Bi₂₀Br₁₆ = Bi₈²⁺Bi₉⁵⁺[BiBr₅]^2–[Bi₂Br₁₁]^5–. Bi₅Br₄ is the bismuth-richest among the bismuth subhalides containing isolated polycations. Extensive differential scanning calorimetry studies indicate that Bi₅Br₄ decomposes at 262 °C, i.e. one degree below the bismuth-rich eutectic at 263 °C. All attempts towards a rational synthesis yielded predominantly the neighboring phases BiBr and Bi₆Br₇.     

Growth,optical, photoluminescence,dielectric, second and third order nonlinear optical studies of benzoyl valine acentric crystal

A nonlinear optical material benzoyl valine (BV) was synthesized by the technique of slow evaporation process at room temperature. The single crystal X ray diffraction analysis evince that crystal corresponds to acentric space group P₂₁ with monoclinic system. The diverse optical properties assured an elevated transparency in BV crystal. Photoluminescence profile revealed the suitability of crystal for fabricating violet lasers. The Laser damage threshold and the dielectric behavior of the grown crystal were analyzed to indicate its practical applications. The second and third order nonlinear optical measurements were studied to prove its potentiality in the domain of nonlinear optical applications.