Zwitterion radicals and anion radicals from electron transfer and solvent condensation with the fingerprint developing agent ninhydrin.

Ninhydrin (the fingerprint developing agent) spontaneously dehydrates in liquid ammonia and in hexamethylphosphoramide (HMPA) to form indantrione, which has a sufficiently large solution electron affinity to extract an electron from the solvent (HMPA) to produce the indantrione anion radical. In liquid NH(3), the presence of trace amounts of amide ion causes the spontaneous formation of an anion radical condensation product, wherein the no. 2 carbon (originally a carbonyl carbon) becomes substituted with -NH(2) and -OH groups. In HMPA, the indantrione anion radical spontaneously forms condensation products with the HMPA to produce a variety of zwitterionic radicals, wherein the no. 2 carbon becomes directly attached to a nitrogen of the HMPA. The mechanisms for the formation of the zwitterionic paramagnetic condensation products are analogous to that observed in the reaction of ninhydrin with amino acids to yield Ruhemann's Purple, the contrast product in fingerprint development. The formation of anion and zwitterionic radical condensation products from ninhydrin and nitrogen-containing solvents may represent an example of a host of analogous polyketone-solvent reactions.     

The Mass Spectrometry of Helical Unfolding in Peptides

Two model peptides, melittin and a growth hormone releasing factor (GRF) analog, have been studied by mass spectrometry and tandem mass spectrometry during the course of their deuterium exchange. Both peptides are known from previous work to form α-helices in solution. When the peptides are exposed to deuterated solvents, their masses increase as deuterium atoms replace protons in the exchangeable sites of the peptides. The mass spectrometry results clearly indicate multiple populations of exchangeable protons: Some exchange very fast, and are presumably on the surface and not involved in hydrogen bonding; others exchange much more slowly, indicating that they are probably participating in hydrogen bonding. Tandem mass spectrometric experiments were conducted, and the masses of the product (fragment) ions were used to determine where in the peptide the deuterium atoms were incorporated. The results agree very well with NMR studies of the same peptides. Melittin appears as two helical segments with a kink around Pro-14. The GRF analog contains a single long helix, spanning almost the entire length of the peptide. The dynamics of the unfolding of the helices can also be explored by observing how the exchange progresses with time.     

A non-Archimedean Ohsawa–Takegoshi extension theorem

Mathematische Zeitschrift - We prove an Ohsawa–Takegoshi-type extension theorem on the Berkovich closed unit disc over certain non-Archimedean fields. As an application, we establish a...     

π-Selective stationary phases: (II) Adsorption behaviour of substituted aromatic compounds on n-alkyl-phenyl stationary phases

The frontal analysis method was used to measure the adsorption isotherms of phenol, 4-chlorophenol, p-cresol, 4-methoxyphenol and caffeine on a series of columns packed with home-made alkyl-phenyl bonded silica particles. These ligands consist of a phenyl ring tethered to the silica support via a carbon chain of length ranging from 0 to 4 atoms. The adsorption isotherm models that fit best to the data account for solute–solute interactions that are likely caused by π–π interactions occurring between aromatic compounds and the phenyl group of the ligand. These interactions are the dominant factor responsible for the separation of low molecular weight aromatic compounds on these phenyl-type stationary phases. The saturation capacities depend on whether the spacer of the ligands have an even or an odd number of carbon atoms, with the even alkyl chain lengths having a greater saturation capacity than the odd alkyl chain lengths. The trends in the adsorption equilibrium constant are also significantly different for the even and the odd chain length ligands.     

Dielectric behaviour of copolymers based on 2,2,2-trifluoroethyl methacrylate and cyano co-monomers

In the frame of a research aiming at developing new dielectric polymers containing CCN and CF substituents with strong dipole moment, statistical copolymers based on cyano monomers such as acrylonitrile (AN), methacrylonitrile (MAN), methylvinylidene cyanide (MVCN) and 2,2,2-trifluoroethylmethacrylate (MATRIF), were synthesized and characterized. Elemental analysis has shown that the molar percentages of AN and MAN in the copolymers were 45 mol.%, while only 5 mol.% of MVCN was incorporated in the poly(MVCN-co-MATRIF) copolymer. These copolymers exhibit glass transition temperatures, T_g, in the range of 70-90 °C. The dynamic dielectric analyses and their complex permittivities of these copolymers were studied versus the temperature and the frequency. Evidence of an α-relaxation phenomenon in the glass transition region, which is confirmed by the Vogel-Fulcher-Tammann (VFT) temperature dependence of the relaxation times, was assigned to the cooperative reorientation motions of the cyano groups. The values of dielectric strength (Δε) for the copolymers based on MATRIF were determined by Havriliak-Negami (HN) fitting from the dispersion curves, and can be related to the polarity of the monomer unit and to the packing of the macromolecular chains. These relaxations are sometimes overlapped by conduction phenomena due to ionic impurities at low frequencies and high temperatures dipolar losses. In the glassy state, the permittivity values of AN and MAN copolymers show an increase of polarity which makes them candidates for some applications amongst advanced electrical materials such as dielectric layer for capacitors.     

First experiments on the Australian Synchrotron Imaging and Medical beamline,including investigations of the effective source size in respect of X‐ray imaging

The Imaging and Medical beamline at the Australian Synchrotron achieved `first light' in December 2008. Here, the first experiments performed on the beamline are reported, which involved both X‐ray imaging and tomography studies for a range of samples. The use of a plastic‐edge phantom for quantitative measurements of contrast and resolution proved to be very instructive and helped to confirm certain parameter values such as the effective horizontal source size, detector resolution and average X‐ray energy for the polychromatic beam.     

Light beats the spread: “non‐diffracting” beams

“Non‐diffracting” beams do not spread as they propagate. This property is useful in many areas. Here, the theory, generation, properties, and applications of various “non‐diffracting” beams, including the Bessel beam, Mathieu beam, and Airy beam is reviewed. Applications include imaging, micromanipulation, nonlinear optics, and optical transfection.     

A Quasi-isometric embedding into the group of Hamiltonian diffeomorphisms with Hofer’s metric

We construct an embedding Φ of [0, 1]^∞ into Ham(M, ω), the group of Hamiltonian diffeomorphisms of a suitable closed symplectic manifold (M, ω). We then prove that Φ is in fact a quasi-isometry. After imposing further assumptions on (M, ω), we adapt our methods to construct a similar embedding of ? ⊕ [0, 1]^∞ into either Ham(M, ω) or

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, the universal cover of Ham(M, ω). Along the way, we prove results related to the filtered Floer chain complexes of radially symmetric Hamiltonians. Our proofs rely heavily on a continuity result for barcodes (as presented in [28]) associated to filtered Floer homology viewed as a persistence module.

     

A sparse Laplacian in tensor product wavelet coordinates

We construct a wavelet basis on the unit interval with respect to which both the (infinite) mass and stiffness matrix corresponding to the one-dimensional Laplacian are (truly) sparse and boundedly invertible. As a consequence, the (infinite) stiffness matrix corresponding to the Laplacian on the n-dimensional unit box with respect to the n-fold tensor product wavelet basis is also sparse and boundedly invertible. This greatly simplifies the implementation and improves the quantitative properties of an adaptive wavelet scheme to solve the multi-dimensional Poisson equation. The results extend to any second order partial differential operator with constant coefficients that defines a boundedly invertible operator.     

Functional Annotation of <Emphasis Type="Italic">Fibrobacter succinogenes</Emphasis> S85 Carbohydrate Active Enzymes

Fibrobacter succinogenes is a cellulolytic bacterium that degrades plant cell wall biomass in ruminant animals and is among the most rapidly fibrolytic of all mesophilic bacteria. The complete genome sequence of Fisuc was completed by the DOE Joint Genome Institute in late 2009. Using new expression tools developed at Lucigen and C5-6 Technologies and a multi-substrate screen, 5,760 random shotgun expression clones were screened for biomass-degrading enzymes, representing 2× genome expression coverage. From the screen, 169 positive hits were recorded and 33 were unambiguously identified by sequence analysis of the inserts as belonging to CAZy family genes. Eliminating duplicates, 24 unique CAZy genes were found by functional screening. Several previously uncharacterized enzymes were discovered using this approach and a number of potentially mis-annotated enzymes were functionally characterized. To complement this approach, a high-throughput system was developed to clone and express all the annotated glycosyl hydrolases and carbohydrate esterases in the genome. Using this method, six previously described and five novel CAZy enzymes were cloned, expressed, and purified in milligram quantities.