Investigation into the ROMP copolymerization of peptide‐ and PEG‐functionalized norbornene derivatives

The ring‐opening metathesis polymerizations (ROMP), using RuCl₂ (PCy₃)₂CHPh, of a series of peptide‐functionalized norbornene derivatives have been investigated. Incorporation of a PEG‐monomer was found to prevent premature precipitation of polymer strands during the course of polymerization reactions and yield water compatible polymers in high conversions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3178–3190, 2007     

Adhesive bonding of glassy polymer surfaces by an ultrathin layer of a semicrystalline polymer

To develop a greater understanding of interfacial interactions between a semicrystalline polymer and a glassy polymer, adhesion tests were performed on very thin layers of poly(ethylene oxide) (PEO) sandwiched between two layers of poly(tetramethyl bisphenol A polycarbonate) (TMPC). The tests were designed to provide intimate contact between the surfaces while they were heated above the melting point of the PEO and cooled back to room temperature. A contact mechanics approach, based on the Johnson, Kendall, and Roberts theory, was used to determine values of the energy release rate describing the energetic driving force for crack propagation within the interfacial region. The ability to measure crack propagation at large values of the energy release rate was limited by rupture of the silicone elastomer that was used to provide a sufficiently compliant matrix for the adhesion experiment. By cycling the tensile stress at relatively low loading levels, we were able to measure fatigue crack propagation at values of the energy release rate that did not result in failure of the elastomer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3809–3821, 2004     

Characterization of N-terminal processing of group VIA phospholipase A<Subscript>2</Subscript> and of potential cleavage sites of amyloid precursor protein constructs by automated identification of signature peptides in LC/MS/MS analyses of proteolytic digests

Dysregulation of proteolytic processing of the amyloid precursor protein (APP) contributes to the pathogenesis of Alzheimer's Disease, and the Group VIA phospholipase A(2) (iPLA(2)beta) is the dominant PLA(2) enzyme in the central nervous system and is subject to regulatory proteolytic processing. We have identified novel N-terminal variants of iPLA(2)beta and previously unrecognized proteolysis sites in APP constructs with a C-terminal 6-myc tag by automated identification of signature peptides in LC/MS/MS analyses of proteolytic digests. We have developed a Signature-Discovery (SD) program to characterize protein isoforms by identifying signature peptides that arise from proteolytic processing in vivo. This program analyzes MS/MS data from LC analyses of proteolytic digests of protein mixtures that can include incompletely resolved components in biological samples. This reduces requirements for purification and thereby minimizes artifactual modifications during sample processing. A new algorithm to generate the theoretical signature peptide set and to calculate similarity scores between predicted and observed mass spectra has been tested and optimized with model proteins. The program has been applied to the identification of variants of proteins of biological interest, including APP cleavage products and iPLA(2)beta, and such applications demonstrate the utility of this approach.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

Characterising ontogenetic niche shifts in Nile crocodile using stable isotope (δ13C, δ15N) analyses of scute keratin

Nile crocodiles undergo a three to five order of magnitude increase in body size during their lifespan. This shift coincides with a change in resource and habitat use which influences the strength, type and symmetry of interactions with other species. Identifying size-specific crocodile groups displaying similar traits is important for conservation planning. Here, we illustrate how stable carbon (δ¹³ C) and nitrogen (δ¹⁵ N) isotope analysis of scute keratin, together with breakpoint modelling analysis can be used to characterise ontogenetic niche shifts. Using a sample set of 238 crocodiles from the Okavango Delta, Botswana (35–463 cm total length), we found prominent size-related changes in the scute keratin δ¹³ C and δ¹⁵ N profiles close to 40 and 119 cm snout-vent length. The first shift corroborated the findings of a traditional stomach-content study conducted on the same population at the same time, and the second conformed to known crocodile ecology. This approach can be used as a first approximation to identify size-specific groups within crocodile populations, and these can then be investigated further using isotopic or other methods.     

Neural control of vocalization: Respiratory and emotional influences

Previous research has shown that a region of the midbrain, the periaqueductal gray matter (PAG), is critical for vocalization. In this review, we describe the results of previous investigations in which we sought to find out how PAG neurons integrate the activity and precise timing of respiratory, laryngeal, and oral muscle activity for natural-sounding vocalization using the technique of excitatory amino acid microinjections in cats. In these studies, all surgical procedures were carried out under deep anaesthesia. In the precollicular decerebrate cat two general types of vocalization, classified as voiced and unvoiced, could be evoked by exciting neurons in the lateral part of the intermediate part of the PAG. The patterns of evoked electromyographic activity were strikingly similar to previously reported patterns of human muscle activity. Coordinated patterns of activity were evoked with just-threshold excitation leading to the conclusion that patterned muscle activity corresponding to the major categories of voiced and voiceless sound production are represented in the PAG. In a parallel series of human and animal experiments, we also determined that the speech and vocalization respiratory patterns are integrated and coordinated with afferent signals related to lung volume. These data have led to the proposal of a new hypothesis for the neural control of vocalization: that the PAG is a crucial brain site for mammalian voice production, not only in the production of emotional or involuntary sounds, but also as a generator of specific respiratory and laryngeal motor patterns essential for human speech and song     

Search for the standard model Higgs boson in the diphoton decay channel with 4.9 fb(-1) of pp collision data at √s=7 TeV with ATLAS

A search for the standard model Higgs boson is performed in the diphoton decay channel. The data used correspond to an integrated luminosity of 4.9 fb(-1) collected with the ATLAS detector at the Large Hadron Collider in proton-proton collisions at a center-of-mass energy of √s=7 TeV. In the diphoton mass range 110-150 GeV, the largest excess with respect to the background-only hypothesis is observed at 126.5 GeV, with a local significance of 2.8 standard deviations. Taking the look-elsewhere effect into account in the range 110-150 GeV, this significance becomes 1.5 standard deviations. The standard model Higgs boson is excluded at 95% confidence level in the mass ranges of 113-115 GeV and 134.5-136 GeV.     

Search for scalar bottom quark pair production with the ATLAS detector in pp collisions at sqrt[s]=7 TeV

The results of a search for pair production of the scalar partners of bottom quarks in 2.05 fb(-1) of pp collisions at sqrt[s]=7 TeV using the ATLAS experiment are reported. Scalar bottom quarks are searched for in events with large missing transverse momentum and two jets in the final state, where both jets are identified as originating from a bottom quark. In an R-parity conserving minimal supersymmetric scenario, assuming that the scalar bottom quark decays exclusively into a bottom quark and a neutralino, 95% confidence-level upper limits are obtained in the b(1) - χ(1)(0) mass plane such that for neutralino masses below 60 GeV scalar bottom masses up to 390 GeV are excluded.