The role of polymer compatibility in the adhesion between surfaces saturated with modified dextrans

Wet and dry adhesion between dextran-coated surfaces were measured aiming to understand the influence of polymer compatibility. The wet adhesion measurements were performed using the atomic force microscope (AFM) colloidal probe technique whereas the dry adhesion measurements were performed using the micro adhesion measurement apparatus (MAMA). Two types of dextrans were used, one cationically modified dextran (DEX) and one that was both cationically and hydrophobically modified (HDEX), leading to three different combinations of polymer-coated surfaces; (1) DEX:DEX, (2) HDEX:DEX, and (3) HDEX:HDEX. DEX increased dry adhesion more than HDEX did, which likely is due to differences in the ability to form specific interactions, especially hydrogen bonding. HDEX gave strong wet adhesion, probably due to its poorer solvency, while DEX contributed to reducing the wet adhesion due to its hydrophilicity. All combinations showed a steric repulsion on approach in aqueous media. Furthermore, when HDEX was adsorbed on either or both surfaces a long range attractive force between the surfaces was detected outside this steric regime.     

Identification of proteins directly from tissue: in situ tryptic digestions coupled with imaging mass spectrometry

A novel method for on-tissue identification of proteins in spatially discrete regions is described using tryptic digestion followed by matrix-assisted laser desorption/ionization (MALDI) imaging mass spectrometry (IMS) with MS/MS analysis. IMS is first used to reveal the protein and peptide spatial distribution in a tissue section and then a serial section is robotically spotted with small volumes of trypsin solution to carry out in situ protease digestion. After hydrolysis, 2,5-Dihydroxybenzoic acid (DHB) matrix solution is applied to the digested spots, with subsequent analysis by IMS to reveal the spatial distribution of the various tryptic fragments. Sequence determination of the tryptic fragments is performed using on-tissue MALDI MS/MS analysis directly from the individual digest spots. This protocol enables protein identification directly from tissue while preserving the spatial integrity of the tissue sample. The procedure is demonstrated with the identification of several proteins in the coronal sections of a rat brain.     

An Ortho-Tetraphenylene-Based “Geländer” Architecture Consisting Exclusively of 52 sp2-Hybridized C Atoms

A new type of “Geländer” molecule based on a ortho-tetraphenylene core is presented. The central para-quaterphenyl backbone is wrapped by a 4,4’-di((Z)-styryl)-1,1’-biphenyl banister, with its aryl rings covalently attached to all four phenyl rings of the backbone. The resulting helical chiral bicyclic architecture consists exclusively of sp²-hybridized carbon atoms. The target structure was assembled by expanding the central ortho-tetraphenylene subunit with the required additional phenyl rings followed by a twofold macrocyclization. The first macrocyclization attempts based on a twofold McMurry coupling were successful but low yielding; the second strategy, profiting from olefin metathesis, provided satisfying yields. Hydrogenation of the olefins resulted in a saturated derivative of similar topology, thereby allowing the interdependence between saturation and physico-chemical properties to be studied. The target structures, including their solid-state structures, were fully characterized. The helical chiral bicycle was synthesized as a racemate and separated into pure enantiomers by HPLC on a chiral stationary phase. Comparison of recorded and simulated chiroptical properties allowed the enantiomers to be assigned.     

Experimental assessment of a large sample cell for laser ablation-ICP-MS, and its application to sediment core micro-analysis

The coupling of laser ablation (LA) to inductively coupled plasma-mass spectrometry (ICP-MS) enables the direct analysis of solid samples with micrometric resolution. Analysis is often restricted to relatively small samples owing to the dimensions of conventional ablation cells. Here, we assess the performance of a large rectangular, commercially-available sample cell which enables analysis over a 10.2?×?5.2 cm² area. Comparison with the conventional cell shows a small to moderate performance decrease for the large cell resulting from the dilution of ablated particles in a larger volume with a 4–31% lower signal output and longer signal tailings. The performance of this cell is however sufficient for the determination of both major and trace elements in many kinds of samples. The applicability of the large cell LA-ICP-MS setup was demonstrated by the determination of Al, Si, Mn, Fe, Cu, Zn Pb and U in sediment core sections at a resolution of 0.6 mm. Detection limits for sediment analysis were 7 mg Al kg^?1, 68 mg Si kg^?1, 0.5 mg Mn kg^?1, 20 mg Fe kg^?1, 0.2 mg Cu kg^?1, 0.3 mg Zn kg^?1, 0.08 mg Pb kg^?1 and 0.003 mg U kg^?1. Cyclic patterns, which would have been overlooked by conventional analysis at cm resolution, were observed in analysed sediments. This study demonstrates the potential of LA-ICP-MS in environmental analysis, with the large sample cell setup offering the possibility to analyse a wider range of samples without sectioning.     

Denseness of volatile and nonvolatile sequences of functions

In a recent paper by Jonasson and Steif, definitions to describe the volatility of sequences of Boolean functions, $f_n:{\{?1,1\}}^n\to \{?1,1\}$ were introduced. We continue their study of how these definitions relate to noise stability and noise sensitivity. Our main results are that the set of volatile sequences of Boolean functions is a natural way “dense” in the set of all sequences of Boolean functions, and that the set of non-volatile Boolean sequences is not “dense” in the set of noise stable sequences of Boolean functions.     

Photochemistry of bromofluorobenzenes

The photochemistry of low lying excited states of six different fluorinated bromobenzenes has been investigated by means of femtosecond laser spectroscopy and high level ab initio CASSCF/CASPT2 quantum chemical calculations. The objective of the work was to investigate how and to what extent light substituents, position on the benzene ring and number, would influence the dissociation mechanism of bromobenzene. In general, the actual position of a fluorine atom affects the dissociation rate to a less extent than the number of fluorine atoms. A clear connection between a lowering of a repulsive pisigma relative to a bound pipi state and the number of fluorine substituents exists, and the previously suggested model of coupling between dissociation rate and relative location of bound and repulsive state still holds for these molecules. A more elaborate examination of the electronic structure of the excited states in bromobenzenes than previously reported is presented.     

Role of the phase transition at GaN QDs formation on (0001)AlN surface by ammonia molecular beam epitaxy

Journal of Thermal Analysis and Calorimetry - We report an original method of GaN/AlN quantum dots (QDs) formation with low density by ammonia MBE on the (0001)AlN...