Synthesis and characterization of an MRI Gd‐based probe designed to target the translocator protein

DPA‐713 is the lead compound of a recently reported pyrazolo[1,5‐a]pyrimidineacetamide series, targeting the translocator protein (TSPO 18 kDa), and as such, this structure, as well as closely related derivatives, have been already successfully used as positron emission tomography radioligands. On the basis of the pharmacological core of this ligands series, a new magnetic resonance imaging probe, coded DPA‐C₆‐(Gd)DOTAMA was designed and successfully synthesized in six steps and 13% overall yield from DPA‐713. The Gd‐DOTA monoamide cage (DOTA = 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid) represents the magnetic resonance imaging reporter, which is spaced from the phenylpyrazolo[1,5‐a]pyrimidineacetamide moiety (DPA‐713 motif) by a six carbon‐atom chain. DPA‐C₆‐(Gd)DOTAMA relaxometric characterization showed the typical behavior of a small‐sized molecule (relaxivity value: 6.02 mM^?1 s^?1 at 20 MHz). The good hydrophilicity of the metal chelate makes DPA‐C₆‐(Gd)DOTAMA soluble in water, affecting thus its biodistribution with respect to the parent lipophilic DPA‐713 molecule. For this reason, it was deemed of interest to load the probe to a large carrier in order to increase its residence lifetime in blood. Whereas DPA‐C₆‐(Gd)DOTAMA binds to serum albumin with a low affinity constant, it can be entrapped into liposomes (both in the membrane and in the inner aqueous cavity). The stability of the supramolecular adduct formed by the Gd‐complex and liposomes was assessed by a competition test with albumin. Copyright © 2013 John Wiley & Sons, Ltd.     

Variational technique and principal solution in half-linear oscillation criteria

We investigate oscillatory properties of half-linear differential equations. The investigated half-linear equation is viewed as a perturbation of another (nonoscillatory) equation of the same form and perturbation is allowed both in the absolute term and in the derivative term. First, the Sturmian type theorem for solutions of the associated Riccati equation is established. In the second part of the paper we prove new half-linear oscillation criteria using the variational technique.     

Study of latent fingermarks by matrix‐assisted laser desorption/ionisation mass spectrometry imaging of endogenous lipids

Identification of suspects via fingermark analysis is one of the mainstays of forensic science. The success in matching fingermarks, using conventional fingermark scanning and database searching, strongly relies on the enhancement method adopted for fingermark recovery; this in turn depends on the components present in the fingermarks, which will change over time. This work aims to develop a robust methodology for improved analytical detection of the fingermark components. For the first time, matrix‐assisted laser desorption/ionisation mass spectrometry imaging (MALDI‐MSI) has been used to image endogenous lipids from fresh and aged, groomed and ungroomed fingermarks. The methodology was initially developed using oleic acid which was detected along with its degradation products over a 7‐day period, at three different temperatures in a time‐course experiment. The optimised methodology was then transferred to the imaging analysis of real fingermark samples. Fingermark patterns were reconstructed by retrieving the m/z values of oleic acid and its degradation products. This allowed the three aged fingermarks to be distinguished. In order to prove that MALDI‐MSI can be used in a non‐destructive way, a simple washing protocol was adopted which returned a fingermark that could be further investigated with classical forensic approaches. The work reported here proves the potential and the feasibility of MALDI‐MSI for the forensic analysis of fingermarks, thus making it competitive with other MSI techniques such as desorption electrospray ionisation (DESI)‐MS. The feasibility of using MALDI‐MSI in fingermark ageing studies is also demonstrated along with the potential to be integrated into routine fingermark forensic analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Poly(dimethylaminoethylmethacrylate) hydrochloride (PDMAEM-HCl) a well behaving polycation for multilayer formation on planar surfaces

The polycation preparation of poly(dimethylaminoethylmethacrylate) hydrochloride and the multilayer formation in combination with poly(sodium 4-styrenesulphonate) as polyanion studies onto different substrates, as followed by streaming potential measurements, in situ surface plasmon resonance spectroscopy, and multi-wavelength ellipsometry, are reported. Furthermore, we studied the resulting multilayer buildup of dry surfaces by UV-Vis spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy measurements. Thereby, the layer built up at the solid/liquid-interface could be followed and quantified at the molecular level.This revised version was published online in April 2005 with corrections to the article category.     

Design and electro-optical characterization of Si-based resonant cavity light emitting devices at 850 nm

We report on the fabrication and characterization of Si/SiO₂ Fabry-Perot microcavities. These structures are used to enhance the external quantum efficiency along the cavity axis and the spectral purity of emission from silicon rich oxide films that are used as active media to fabricate a Si based RCLED (resonant cavity light emitting devices). A new structure to electrically pump the active media in the resonant cavity has been designed. These structures are fabricated by chemical vapour deposition on a silicon substrate. The microcavities are tuned at 850 nm and present a quality factor ranging from 17 to 150 depending on the number of pairs constituting the dielectric mirrors. An enhancement of the electro and photoluminescence (PL) signal of 20 times is achieved for the selected emission wavelength. These cavities are characterized by TEM analysis to evaluate film uniformity, thicknesses and the densification after annealing processes for temperature ranging from 800 to 1100 °C. The electrical properties of the active media are analyzed. The electroluminescence spectral features are compared with PL spectra correlated with the quality factor of the cavities. The photometric diagram shows also a high directionality of the emitted light within a 30° cone from the sample normal.     

Chemoselective Alkene Hydrosilylation Catalyzed by Nickel Pincer Complexes

Chemoselective hydrosilylation of functionalized alkenes is difficult to achieve using base‐metal catalysts. Reported herein is that well‐defined bis(amino)amide nickel pincer complexes are efficient catalysts for anti‐Markovnikov hydrosilylation of terminal alkenes with turnover frequencies of up to 83 000 per hour and turnover numbers of up to 10 000. Alkenes containing amino, ester, amido, ketone, and formyl groups are selectively hydrosilylated. A slight modification of reaction conditions allows tandem isomerization/hydrosilylation reactions of internal alkenes using these nickel catalysts.     

Discriminantal arrangement, 3 × 3 minors of Plücker matrix and hypersurfaces in Grassmannian Gr(3,n)

We show that points in specific degree-2 hypersurfaces in the Grassmannian $Gr(3,n)$ correspond to generic arrangements of n hyperplanes in ${\mathbb{C}}^3$ with associated discriminantal arrangement having intersections of multiplicity three in codimension two.     

Feedback Stabilization for a Scalar Conservation Law with PID Boundary Control

This paper deals with a scalar conservation law in 1-D space dimension, and in particular, the focus is on the stability analysis for such an equation. The problem of feedback stabilization under proportional-integral-derivative (PID for short) boundary control is addressed. In the proportional-integral (PI for short) controller case, by spectral analysis, the authors provide a complete characterization of the set of stabilizing feedback parameters, and determine the corresponding time delay stability interval. Moreover, the stability of the equilibrium is discussed by Lyapunov function techniques, and by this approach the exponential stability when a damping term is added to the classical PI controller scheme is proved. Also, based on Pontryagin results on stability for quasipolynomials, it is shown that the closed-loop system subject to PID control is always unstable.