Synthesis of pyranosyl amidoximes by addition of amines to pyranosyl nitrile oxides

Addition of amines to pyranosyl nitrile oxides, generated by base-induced dehydrochlorination of the corresponding hydroximoyl chloride, affords pyranosyl N-alkyl/aryl-formamide oximes (41-90%). Reaction with amino acid esters yields the corresponding amidoximes and/or 3-pyranosyl-1,2,4-oxadiazin-6-ones. The structure of N-phenyl-C-(2,3,4-tri-O-acetyl-β-D-xylopyranosyl)formamide oxime was established by X-ray crystallography.     

A computational study of the reactions of a beta-diketiminatoaluminium(I) complex with the hydrogen atom and the electron

A computational study has been performed to examine the reactions of a model beta-diketiminatoaluminium (I) complex with the hydrogen atom and with the electron. It was found that the hydrogen atom adds to the metal centre exothermically (DeltaH(rxn)=-202 kJ mol(-1)), and the spin density in the resulting radical resides entirely on the beta-diketiminato ligand. The spin density of the corresponding radical anion is very similar to the H-adduct.     

Lamination method for the study of interfaces in polymeric thin film transistors

A method for the fabrication of polymeric thin-film transistors (TFTs) by lamination is described. Poly(dimethylsiloxane) stamps were used to delaminate thin films of semiconducting polymers from silicon wafers coated with a self-assembled monolayer (SAM) formed from octyltrichlorosilane. These supported films were laminated onto electrode structures to form coplanar TFTs. The fabrication process was used to make TFTs with poly(3-hexylthiophene), P3HT, and poly[5,5'-bis(3-dodecyl-2-thienyl)-2,2'-bithiophene], PQT-12. TFTs, where these polymers were laminated onto gate dielectrics coated with SAMs from octyltrichlorosilane, had effective field-effect mobilities of 0.03 and 0.005 cm2/(V s), respectively. TFTs where PQT-12 was laminated onto gate dielectrics that were not coated with a SAM also had mobility of 0.03 cm2/(V s). In contrast, TFTs fabricated by spin-coating PQT-12 onto the same structure had mobilities ranging from 10-3 to 10-4 cm2/(V s). These results suggest that the lower mobilities of polymer TFTs made with hydrophilic gate dielectrics are caused by molecular ordering in the semiconducting film rather than electronic effects of dipolar groups at the interface.     

Targeting structural features of viral genomes with a nano-sized supramolecular drug

RNA targeting is an exciting frontier for drug design. Intriguing targets include functional RNA structures in structurally-conserved untranslated regions (UTRs) of many lethal viruses. However, computational docking screens, valuable in protein structure targeting, fail for inherently flexible RNA. Herein we harness MD simulations with Markov state modeling to enable nanosize metallo-supramolecular cylinders to explore the dynamic RNA conformational landscape of HIV-1 TAR untranslated region RNA (representative for many viruses) replicating experimental observations. These cylinders are exciting as they have unprecedented nucleic acid binding and are the first supramolecular helicates shown to have anti-viral activity in cellulo: the approach developed in this study provides additional new insight about how such viral UTR structures might be targeted with the cylinder binding into the heart of an RNA-bulge cavity, how that reduces the conformational flexibility of the RNA and molecular details of the insertion mechanism. The approach and understanding developed represents a new roadmap for design of supramolecular drugs to target RNA structural motifs across biology and nucleic acid nanoscience.

MD simulations and Markov state modeling explore induced fit binding of metallo-helicates to bulges in dynamic TAR RNA, reproduce experimental data, show how RNA conformational flexibility is reduced, and give mechanistic insight into insertion.     

Minimax risk overl p -balls forl p -error

Summary Consider estimating the mean vector from dataN _n (, ² I) withl _q norm loss,q1, when is known to lie in ann-dimensionall _p ball,p(0, ). For largen, the ratio of minimaxlinear risk to minimax risk can bearbitrarily large ifp. Obvious exceptions aside, the limiting ratio equals 1 only ifp=q=2. Our arguments are mostly indirect, involving a reduction to a univariate Bayes minimax problem. Whenp, simple non-linear co-ordinatewise threshold rules are asymptotically minimax at small signal-to-noise ratios, and within a bounded factor of asymptotic minimaxity in general. We also give asymptotic evaluations of the minimax linear risk. Our results are basic to a theory of estimation in Besov spaces using wavelet bases (to appear elsewhere).     

On the Parametrization of the Afocal Stable Distributions

Thanks to Hall's documentation of a situation he described asa ‘Comedy of errors’ in the earlier literature onstable distributions, there is now general agreement as to theparametrization of these distributions when standardized asto location and scale. However, two subtly different parametrizationsof location and scale remain current in the afocal stable cases,defined as those with characteristic exponent = 1 and skewnessparameter ß 0. The more widely used parametrization,adopted by Hall and two recent monographs, lacks the linearityproperty that is ordinarily expected of location and scale parameters.This note shows that the alternative parametrization has thislinearity property, and compares the implications of the twoparametrizations for properties of stable distributions. A thirdrecent monograph seeks to avoid these issues by denying thatthe afocal stable distributions are stable at all, but it isshown that they are, in fact, integral members of the stablefamily.     

Unusual selectivity of unprotected aziridines in palladium-catalyzed allylic amination enables facile preparation of branched aziridines

Functionalized branched aziridines can be prepared in high yields and with high levels of regioselectivity using unprotected aziridines as nitrogen sources in palladium-catalyzed allylic amination. High levels of enantioselectivity can be achieved with BINAP on palladium. This methodology allows for strategic placement of an aziridine-containing fragment within a complex molecule environment for further elaboration.     

The first structural and spectroscopic characterization of a neptunyl polyoxometalate complex

The reaction between PW9O349- and NpO2+ has yielded the first structurally characterized neptunyl(V) polyoxometalate complex, [Na2(NpO2)2(A-PW9O34)2]14-. This complex is isostructural with the uranyl(VI) analogue, and there is also spectroscopic evidence for its existence in solution. The complex is readily extracted into toluene, and this may have significance in the sequestering and/or separation of the neptunyl ion in terms of nuclear waste management.     

Structural characterization of a lanthanum bistriflimide complex, La(N(SO2CF3)2)3(H2O)3, and an investigation of La, Sm, and Eu electrochemistry in a room-temperature ionic liquid, [Me3N(n)Bu][N(SO2CF3)2

The reduction of selected lanthanide cations to the zerovalent state in the room-temperature ionic liquid [Me3N(n)Bu][TFSI] is reported (where TFSI = bistriflimide, [N(SO2CF3)2]-). The lanthanide cations were introduced to the melt as the TFSI hydrate complexes [Ln(TFSI)3(H2O)3] (where Ln = La(III), Sm(III) or Eu(III)). The lanthanum compound [La(TFSI)3(H2O)3] has been crystallographically characterized, revealing the first structurally characterized f-element TFSI complex. The lanthanide in all three complexes was shown to be reducible to the metallic state in [Me3N(n)Bu][TFSI]. For both the Eu and Sm complexes, reduction to the metallic state was achieved via divalent species, and there was an additional observation of the electrodeposition of Eu metal.     

Microstructured cocultures of cardiac myocytes and fibroblasts: a two-dimensional in vitro model of cardiac tissue.

Cardiac myocytes and fibroblasts are essential elements of myocardial tissue structure and function. In vivo, myocytes constitute the majority of cardiac tissue volume, whereas fibroblasts dominate in numbers. In vitro, cardiac cell cultures are usually designed to exclude fibroblasts, which, because of their maintained proliferative potential, tend to overgrow the myocytes. Recent advances in microstructuring of cultures and cell growth on elastic membranes have greatly enhanced in vitro preservation of tissue properties and offer a novel platform technology for producing more in vivo-like models of myocardium. We used microfluidic techniques to grow two-dimensional structured cardiac tissue models, containing both myocytes and fibroblasts, and characterized cell morphology, distribution, and coupling using immunohistochemical techniques. In vitro findings were compared with in vivo ventricular cyto-architecture. Cardiac myocytes and fibroblasts, cultured on intersecting 30-microm-wide collagen tracks, acquire an in vivo-like phenotype. Their spatial arrangement closely resembles that observed in native tissue: Strands of highly aligned myocytes are surrounded by parallel threads of fibroblasts. In this in vitro system, fibroblasts form contacts with other fibroblasts and myocytes, which can support homogeneous and heterogeneous gap junctional coupling, as observed in vivo. We conclude that structured cocultures of cardiomyocytes and fibroblasts mimic in vivo ventricular tissue organization and provide a novel tool for in vitro research into cardiac electromechanical function.