The O-neophyl rearrangement of 1,1-diarylalkoxyl radicals. Experimental evidence for the formation of an intermediate 1-oxaspiro[2,5]octadienyl radical

A product study on the reactivity of a 1,1-diarylalkoxyl radical bearing 2,2-diphenylcyclopropyl groups in the para-positions has been carried out. The exclusive formation of a product deriving from cyclopropyl ring-opening has been observed, indicating that 1,1-diarylalkoxyl radicals exist in equilibrium with a bridged 1-oxaspiro[2,5]octadienyl radical. This represents the first experimental evidence in support of the stepwise nature of the O-neophyl rearrangement of 1,1-diarylalkoxyl radicals.     

Laccase–polyazetidine prepolymer–MWCNT integrated system: Biochemical properties and application to analytical determinations in real samples

Bioelectrochemical properties of Trametes versicolor Laccase (TvL) and Trametes hirsuta Laccase (ThL) immobilized by using polyazetidine prepolymer (PAP) onto multi-walled carbon nanotubes (MWCNTs) screen printed electrode (SPE) surface, have been studied with several redox mediators by cyclic voltammetry (CV). The efficient entrapment of laccase in the PAP layer was confirmed by determination of both kinetic parameters (maximum current and Michaelis–Menten apparent constant) and analytical performances by chronoamperometry. The Laccase-modified MWCNTs electrode provides an effective biosensor for determination of polyphenols and catecholamines in real matrices; performances of the considered biosensors for real samples analysis are also compared and discussed.     

d6 metal systems for white phosphorus activation

This short review describes a breakthrough provided by the synthesis of d⁶ metal complexes containing the intact molecules P₄ and P₄S₃. The coordinated cage molecules acquire unexpected reactivity and undergo dismutation reactions in mild conditions in the presence of water. The outcomings are obtained either in form of free or coordinated molecules; the former are hypophosphorous and phosphorous acids, the latter comprise, besides phosphine, PH₃, such species as thiophosphinous acid, PH₂SH, diphosphane, P₂H₄, 1-hydroxytriphosphane, PH(OH)PHPH₂ and 1,1,4-tris-hydroxytetraphosphane, P(OH)₂PHPHPH(OH), which are either unknown or extremely reactive as free molecules. The formation of the above molecules provides a clue to the hydrolytic activation of the P₄ and P₄S₃ cage molecules.     

Extraction methods of red blood cell membrane proteins for Multidimensional Protein Identification Technology (MudPIT) analysis

Since red blood cells (RBCs) lack nuclei and organelles, cell membrane is their main load-bearing component and, according to a dynamic interaction with the cytoskeleton compartment, plays a pivotal role in their functioning. Even if erythrocyte membranes are available in large quantities, the low abundance and the hydrophobic nature of cell membrane proteins complicate their purification and detection by conventional 2D gel-based proteomic approaches. So, in order to increase the efficiency of RBC membrane proteome identification, here we took advantage of a simple and reproducible membrane sub-fractionation method coupled to Multidimensional Protein Identification Technology (MudPIT). In addition, the adoption of a stringent RBC filtration strategy from the whole blood, permitted to remove exhaustively contaminants, such as platelets and white blood cells, and to identify a total of 275 proteins in the three RBC membrane fractions collected and analysed. Finally, by means of software for the elaboration of the great quantity of data obtained and programs for statistical analysis and protein classification, it was possible to determine the validity of the entire system workflow and to assign the proper sub-cellular localization and function for the greatest number of the identified proteins.     

Behavior of human serum albumin on strong cation exchange resins: II. Model analysis

Experiments with human serum albumin on a strong cation exchange resin exhibit a peculiar elution pattern: the protein elutes with two peaks in a modifier gradient. This behavior is modeled with a general rate model, where the two elution peaks are modeled with two binding conformations, one of which is at equilibrium conditions, while for the other, the adsorption process is rate limited. Isocratic experiments under nonadsorbing conditions were used to characterize the mass transfer process. The isotherm of both adsorption conformations as well as the kinetic of adsorption and desorption for the second conformation are functions of the modifier concentration. They are evaluated with linear modifier gradient experiments and step experiments with various adsorption times. All experimental features are well reproduced by the proposed modified general rate model.     

Measurement of Lamb wave polarization using a one-dimensional scanning laser vibrometer (L)

A single head scanning laser Doppler vibrometer is used for the estimation of the polarization of the first symmetric (S(0)) and antisymmetric (A(0)) Lamb wave modes. The measurements at two known incidence angles are performed in order to resolve the two components of motion. Filtering in the frequency/wavenumber domain of the response recorded along a scan line separates the contributions from each mode and allows the evaluation of the corresponding elliptical trajectories of particle motion. Comparison between measured and analytically estimated trajectories validates the measurement technique and suggests its application for the development of material characterization and diagnostics tools.     

A frequency selective acoustic transducer for directional Lamb wave sensing

A frequency selective acoustic transducer (FSAT) is proposed for directional sensing of guided waves. The considered FSAT design is characterized by a spiral configuration in wavenumber domain, which leads to a spatial arrangement of the sensing material producing output signals whose dominant frequency component is uniquely associated with the direction of incoming waves. The resulting spiral FSAT can be employed both for directional sensing and generation of guided waves, without relying on phasing and control of a large number of channels. The analytical expression of the shape of the spiral FSAT is obtained through the theoretical formulation for continuously distributed active material as part of a shaped piezoelectric device. Testing is performed by forming a discrete array through the points of the measurement grid of a scanning laser Doppler vibrometer. The discrete array approximates the continuous spiral FSAT geometry, and provides the flexibility to test several configurations. The experimental results demonstrate the strong frequency dependent directionality of the spiral FSAT and suggest its application for frequency selective acoustic sensors, to be employed for the localization of broadband acoustic events, or for the directional generation of Lamb waves for active interrogation of structural health.     

Dysregulation of chemo-cytokine production in schizophrenic patients versus healthy controls

Background  

The exact cause of schizophrenia is not known, although several aetiological theories have been proposed for the disease, including developmental or neurodegenerative processes, neurotransmitter abnormalities, viral infection and immune dysfunction or autoimmune mechanisms. Growing evidence suggests that specific cytokines and chemokines play a role in signalling the brain to produce neurochemical, neuroendocrine, neuroimmune and behavioural changes. A relationship between inflammation and schizophrenia was supported by abnormal cytokines production, abnormal concentrations of cytokines and cytokine receptors in the blood and cerebrospinal fluid in schizophrenia. Since the neuropathology of schizophrenia has recently been reported to be closely associated with microglial activation we aimed to determined whether spontaneous or LPS-induced peripheral blood mononuclear cell chemokines and cytokines production is dysregulated in schizophrenic patients compared to healthy subjects. We enrolled 51 untreated first-episode schizophrenics (SC) and 40 healthy subjects (HC) and the levels of MCP-1, MIP-1α, IL-8, IL-18, IFN-γ and RANTES were determined by Elisa method in cell-free supernatants of PBMC cultures.     

4D localization in Randall-Sundrum 2 supergravity and in Vasiliev theories

We discuss the problem of localization of 4D massless states in Randall-Sundrum 2 (one-brane) models. A Randall-Sundrum 2 construction starting from N=8 gauged supergravity in 5D anti-de Sitter space gives rise to an N=4 supergravity-matter system. We explicitly show that only the modes of the N=4 graviton supermultiplet localize on the 4D brane, streamlining and generalizing previous works. We also point out that while charged 1/4 BPS black holes do exist in the 4D theory, they are always produced in sets of total charge zero. This zero-charge configuration uplifts to a 5D metric without naked singularities, thus avoiding the curvature singularity of the 5D uplift of an isolated charged BPS black hole. Finally, we resolve a puzzle with localization of massless high spin fields on a (putative) Randall-Sundrum 2 construction based on Vasiliev?s high spin theories. We show that while high spin fields do localize, the gauge symmetry that ensures decoupling of their unphysical polarizations is anomalous. This implies that the high spin fields must acquire a mass.     

Simple eigenvalues for the Steklov problem in a domain with a small hole. A functional analytic approach

Let be a bounded open domain of . Let denote the outward unit normal of . We assume that the Steklov problem Δu = 0 in and on has a simple eigenvalue of . Then we consider an annular domain obtained by removing from a small‐cavity size of ε > 0, and we show that under proper assumptions there exists a real valued and real analytic function defined in an open neighborhood of (0,0) in and such that is a simple eigenvalue for the Steklov problem Δu = 0 in and on for all ε > 0 small enough, and such that . Here denotes the outward unit normal of , and δ_2,2 ≡ 1 and δ_2,n ≡ 0 if n ≥ 3. Then related statements have been proved for corresponding eigenfunctions. Copyright © 2013 John Wiley & Sons, Ltd.