Structure of bis(2-pyridine-N-oxide) diselenide and its formation from tetraphenylantimony(V)selenopyridine-N-oxide

The structure of bis(2-pyridine-N-oxide) diselenide was determined by single crystal X-ray diffraction. The compound crystallized in the triclinic system and the structure was solved in the space group . The lattice constants were determined to bea=7.174(2),b=7.176(2),c=11.070(2) , =87.67(2)°, =73.68(2)°, and =89.57(2)°;Z=2,D _x=1.906 Mg m^–3. The final least squares refinement based on 1942 independent observed reflections yieldedR=0.033,wR=0.044. The Se–Se bond length is 2.326(1) and each Se is coordinated to the O atom of the corresponding N-oxide moiety at a distance of about 2.6 .     

Invariant Higher-Order Variational Problems

We investigate higher-order geometric k-splines for template matching on Lie groups. This is motivated by the need to apply diffeomorphic template matching to a series of images, e.g., in longitudinal studies of Computational Anatomy. Our approach formulates Euler-Poincaré theory in higher-order tangent spaces on Lie groups. In particular, we develop the Euler-Poincaré formalism for higher-order variational problems that are invariant under Lie group transformations. The theory is then applied to higher-order template matching and the corresponding curves on the Lie group of transformations are shown to satisfy higher-order Euler-Poincaré equations. The example of SO(3) for template matching on the sphere is presented explicitly. Various cotangent bundle momentum maps emerge naturally that help organize the formulas. We also present Hamiltonian and Hamilton-Ostrogradsky Lie-Poisson formulations of the higher-order Euler-Poincaré theory for applications on the Hamiltonian side.     

Hamiltonian differencing of fluid dynamics

By analyzing the Hamiltonian structures of several representations of continuous Lagrangian fluid dynamics, a universal Hamiltonian form is developed which unifies those structures and applies both to the continuous and spatially discrete cases. Then the universal Hamiltonian form is used as a “template” for generating numerical differencing schemes which retain the underlying Hamiltonian structure of the continuous theory. Examples are discussed of these spatial differencing schemes for the Euler equations in one, two, and three dimensions. In one dimension, the nondissipative part of the von Neumann-Richtmeyer scheme is recovered as a special case.     

The use of matrix coating assisted by an electric field (MCAEF) to enhance mass spectrometric imaging of human prostate cancer biomarkers

In this work, we combined a newly developed matrix coating technique – matrix coating assisted by an electric field (MCAEF) and matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) to enhance the imaging of peptides and proteins in tissue specimens of human prostate cancer. MCAEF increased the signal‐to‐noise ratios of the detected proteins by a factor of 2 to 5, and 232 signals were detected within the m/z 3500–37500 mass range on a time‐of‐flight mass spectrometer and with the sinapinic acid MALDI matrix. Among these species, three proteins (S100‐A9, S100‐A10, and S100‐A12) were only observed in the cancerous cell region and 14 proteins, including a fragment of mitogen‐activated protein kinase/extracellular signal‐regulated kinase kinase kinase 2, a fragment of cAMP‐regulated phosphoprotein 19, 3 apolipoproteins (C‐I, A‐I, and A‐II), 2 S100 proteins (A6 and A8), β‐microseminoprotein, tumor protein D52, α‐1‐acid glycoprotein 1, heat shock protein β‐1, prostate‐specific antigen, and 2 unidentified large peptides at m/z 5002.2 and 6704.2, showed significantly differential distributions at the p < 0.05 (t‐test) level between the cancerous and the noncancerous regions of the tissue. Among these 17 species, the distributions of apolipoprotein C‐I, S100‐A6, and S100‐A8 were verified by immunohistological staining. In summary, this study resulted in the imaging of the largest group of proteins in prostate cancer tissues by MALDI‐MS reported thus far, and is the first to show a correlation between S100 proteins and prostate cancer in a MS imaging study. The successful imaging of the three proteins only found in the cancerous tissues, as well as those showing differential expressions demonstrated the potential of MCAEF‐MALDI/MS for the in situ detection of potential cancer biomarkers. Copyright © 2015 John Wiley & Sons, Ltd.     

A novel 1,3,5-tris(alpha,beta,beta-trifluorovinyl)benzene monomer

The reaction of the perfluoroalkenylzinc reagent, CF2=CFZnBr, with 1,3,5-tribromobenzene in the presence of a catalytic amount of Pd(Ph3)4 yielded a novel trifunctional monomer 1,3,5-tris(alpha,beta,beta-trifluorovinyl)benzene (1).     

Nafion hypohalites

The perfluorinated ionomers containing sulfonate groups can be converted to the hypochlorite by reaction of the acid with ClF at low temperature. The hypochlorite can be converted to the hypobromite by reaction with a mixture of Br₂ and Cl₂. In this work Nafion - 511 manufactured by the DuPont Company was utilized. These unique hypohalites allow functionalization of the polymer in a variety of new reactions. Conversions of the Nafion hypobromite to the methyl and trifluoromethyl derivatives are described.     

Micro-interferometric backscatter detection using a diode laser

Micro-interferometric backscatter detection (MIBD) is performed with a simple, folded optical train based on the interaction of a diode laser beam and a fused silica capillary tube allowing for refractive index (RI) determinations and detection of optically active molecules in small volumes. Side illumination of the capillary by a laser produces a 360° fan of scattered light that contains two sets of high contrast interference fringes. These light and dark spots are viewed on a flat plane in the direct backscatter configuration. Signal interrogation for polarimetry is based on quantifying the relative intensities (depth of modulation (DOM)) of adjacent high frequency (HF) interference fringes for polarimetry and relative fringe position for RI detection. Positional changes of the interference pattern extrema (fringes) allow for the determination of Δn at the 10⁻⁷ level or 5.3 pmol or 0.48 ng of solute. The MIBD-RI detection volume is just 5.0 nl. DOM changes allow for optical activity detection limits of 5.7 × 10⁻⁵° (mandelic acid, []²³ = −153°, and D-glucose, []²⁵ = +52.5°), and a 2σ detection limit of 7.5 × 10⁻⁴ M (D-glucose) and 1.14 × 10⁻³ M (R-mandelic acid). The probe volume of MIBD-polarimetry was 38 nl, and within the probed volume at the limit of detection, about 28.7 pmol of mandelic acid or about 43.7 pmol of D-glucose is present. Furthermore, DOM (polarimetry signal) is unchanged when a non-optically active solute is interrogated by the MIBD-polarimeter. Finally, an optical model was derived and used to evaluate the advantages and pitfalls of using diode laser for MIBD.     

Cycloaddition of the Trimethylenemethane-Palladium Complex to Activated Six-Membered and Medium-Ring Enones

2-Carbomethoxycyclohexenones and -0ctenones react with (Z-(acetoxymethyl)-3-allyl)trimethylsilane in the presence of Pd(O) to give methylenecyclopentane cycloadducts in yields ranging from 46–92%. The corresponding 2-methyl derivatives proved far less reactive (only 5% trapping).