Expedient BINOL derivative arylations

A dramatic improvement of our previous methodology based on a Suzuki–Miyaura cross-coupling to access 3,3′-disubstituted H₈-BINOLs using microwave heating is reported herein. These new conditions represent a large gain in term of atom-economy, reaction time, catalyst loading, and excess of reagents employed.     

A Mechanistically and Operationally Simple Route to Metal–N-Heterocyclic Carbene (NHC) Complexes

We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal–N-heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base-assisted concerted process that does not require free NHC formation. The synthetic protocol was found applicable to a number of transition-metal- and main-group-centered NHC compounds and could become the synthetic route of choice to form M–NHC bonds.     

Synthetic methods for polyamine linkers and their application to combinatorial chemistry

Summary Polyamines and polyamine conjugates display a diverse range of important biological functions, ranging from antibiotics to immunosuppressants and glutamate receptor antagonists. For these reasons, polyamines provide an excellent template/scaffold for combinatorial chemistry. In this paper we present methods for the solid-phase immobilisation of polyamines for use in synthetic and combinatorial chemistry and describe how they have been employed in the preparation of a number of important polyamine conjugates and polyamine libraries. Thus, we have designed, synthesised and utilised a number of polyamine linkers for both solution and resin screening combinatorial application.     

SHAH: SHape-Adaptive Haar Wavelets for Image Processing

We propose the shape-adaptive Haar (SHAH) transform for images, which results in an orthonormal, adaptive decomposition of the image into Haar-wavelet-like components, arranged hierarchically according to decreasing importance, whose shapes reflect the features present in the image. The decomposition is as sparse as it can be for piecewise-constant images. It is performed via a stepwise bottom-up algorithm with quadratic computational complexity; however, nearly linear variants also exist. SHAH is rapidly invertible. We show how to use SHAH for image denoising. Having performed the SHAH transform, the coefficients are hard- or soft-thresholded, and the inverse transform taken. The SHAH image denoising algorithm compares favorably to the state of the art for piecewise-constant images. A clear asset of the methodology is its very general scope: it can be used with any images or more generally with any data that can be represented as graphs or networks.     

Metal insulator transition characteristics of macro-size single domain VO2 crystals

The metal insulator transition (MIT) characteristics of macro-size single-domain VO₂ crystal were investigated. At the MIT, the VO₂ crystal exhibited a rectangular shape hysteresis curve, a large change in resistance between the insulating and the metallic phases, in the order of ～10⁵, and a small transition width (i.e. temperature difference before and after MIT) as small as 10^?3°C. These MIT characteristics of the VO₂ crystals are discussed in terms of phase boundary motion and the possibility of controlling the speed of the phase boundary, with change in size of crystal, is suggested.     

Variations in T(2)* and fat content of murine brown and white adipose tissues by chemical-shift MRI

Purpose

The purpose was to compare T₂* relaxation times and proton density fat-fraction (PDFF) values between brown (BAT) and white (WAT) adipose tissue in lean and ob/ob mice.

Materials and Methods

A group of lean male mice (n=6) and two groups of ob/ob male mice placed on similar 4-week (n=6) and 8-week (n=8) ad libitum diets were utilized. The animals were imaged at 3 T using a T₂*-corrected chemical-shift-based water–fat magnetic resonance imaging (MRI) method that provides simultaneous estimation of T₂* and PDFF on a voxel-wise basis. Regions of interest were drawn within the interscapular BAT and gonadal WAT depots on co-registered T₂* and PDFF maps. Measurements were assessed using analysis of variance, Bonferroni-adjusted t test for multigroup comparisons and the Tukey post hoc test.

Results

Significant differences (P<.01) in BAT T₂* and PDFF were observed between the lean and ob/ob groups. The ob/ob animals exhibited longer BAT T₂* and greater PDFF than lean animals. However, only BAT PDFF was significantly different (P<.01) between the two ob/ob groups. When comparing BAT to WAT within each group, T₂* and PDFF values were consistently lower in BAT than WAT (P<.01). The difference was most prominent in the lean animals. In both ob/ob groups, BAT exhibited very WAT-like appearances and properties on the MRI images.

Conclusion

T₂* and PDFF are lower in BAT than WAT. This is likely due to variations in tissue composition. The values were consistently lower in lean mice than in ob/ob mice, suggestive of the former's greater demand for BAT thermogenesis and reflective of leptin hormone deficiencies and diminished BAT metabolic activity in the latter.     

Template-free one-step electrochemical formation of polypyrrole nanowire array

Oriented polypyrrole nanowire (nanorod) array readily forms using one-step pyrrole electropolymerization without using a template. These nanostructures having diameter in the range of 40–120 nm are obtained by electrogenerating polypyrrole in the presence of jointly non-acidic and weak-acidic anions. The latter are essential, their presence leads to the formation of an overoxidized polypyrrole thin layer that surrounds the polypyrrole nanostructure base. This simple and convenient method allows direct polymer nanowire array fabrication on various conductive substrates, the length of nanostructures being controlled by the polymerization time. Finally, a reaction mechanism involving oxidation of pyrrole and water and polypyrrole overoxidation is discussed.     

Protein digestion and phosphopeptide enrichment on a glass microchip

This work describes an integrated glass microdevice for proteomics, which directly couples proteolysis with affinity selection. Initial results with standard phosphopeptide fragments from β-casein in peptide mixtures showed selective capture of the phosphorylated fragments using immobilized metal affinity chromatography (IMAC) beads packed into a microchannel. Complete selectivity was seen with angiotensin, with capture of only the phosphorylated form. On-chip proteolysis, using immobilized trypsin beads packed into a separate channel, was directly coupled to the phosphopeptide capture and the integrated devices evaluated using β-casein. Captured and eluted fragments were analyzed using both capillary electrophoresis (CE) and capillary liquid chromatography/mass spectrometry (cLC/MS). The results show selective capture of only phosphopeptide fragments, but incomplete digestion of the protein was apparent from multiple peaks in the CE separations. The MS analysis indicated a capture bias on the IMAC column for the tetraphosphorylated peptide fragment over the monophosphorylated fragment. Application to digestion and capture of a serum fraction showed capture of material; however, non-specific binding was evident. Additional work will be required to fully optimize this system, but this work represents a novel sample preparation method, incorporating protein digestion on-line with affinity capture for proteomic applications.