Matrix‐assisted laser desorption/ionization tissue profiling of secretoneurin in the nucleus accumbens shell from cocaine‐sensitized rats

Proteins in the nucleus accumbens mediate many cocaine‐induced behaviors. In an effort to measure changes in nucleus accumbens protein expression as potential biomarkers for addiction, coronal tissue sections were obtained from rats that developed behavioral sensitization after daily administration of cocaine, or from daily saline‐treated controls. The tissue sections were subjected to matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry (MS) profiling and tissue imaging. For profiling experiments, brain sections were manually spotted with matrix over the nucleus accumbens, a brain region known to regulate cocaine sensitization. Summed mass spectra (10 000 laser shots, grid) were acquired and spectra were aligned to reference peaks. Using bioinformatics tools, eight spectral features were found to be altered by cocaine treatment. Based on additional sequencing experiments with MALDI tandem MS and database searches of measured masses, secretoneurin (m/z 3653) was identified as having an increased expression. In addition, the distribution of m/z 3653 in the nucleus accumbens was determined by MALDI tissue imaging, and the increased expression of its precursor protein, secretogranin II, was verified by immunoblotting. Copyright © 2009 John Wiley & Sons, Ltd.     

Mechanical activation of catalysts for C-C bond forming and anionic polymerization reactions from a single macromolecular reagent

Coupling of pyridine-capped poly(methyl acrylate)s, PyP(M) (where M corresponds to the number average molecular weight in kDa), to the SCS-cyclometalated dipalladium complex [(1)(CH(3)CN)(2)] afforded organometallic polymers [(1)(PyP(M))(2)] with a concomitant doubling in molecular weight. Ultrasonication of solutions containing [(1)(PyP(M))(2)] effected the mechanical scission of a palladium-pyridine bond, where the liberated PyP(M) was trapped with excess HBF(4) as the corresponding pyridinium salt, harnessed to effect the stoichiometric deprotonation of a colorimetric indicator, or used to catalyze the anionic polymerization of α-trifluoromethyl-2,2,2-trifluoroethyl acrylate. The mechanically induced chain scission also unmasked a catalytically active palladium species which was used to facilitate carbon-carbon bond formation between benzyl cyanide and N-tosyl imines. Spectroscopic and macromolecular analyses as well as a series of control experiments demonstrated that the aforementioned structural changes were derived from mechanical forces that originated from ultrasound-induced dissociation of the polymer chains connected to the aforementioned Pd complexes.     

Biodegradable aliphatic thermoplastic polyurethane based on poly(ε‐caprolactone) and L‐lysine diisocyanate

A biodegradable aliphatic thermoplastic polyurethane based on L ‐lysine diisocyanate and 1,4‐butanediol hard block segments, and 2000 g/mol poly(ε‐caprolactone) diol soft block segments was synthesized. The resulting polymer was a tough thermoplastic with ultimate tensile strength of 33 MPa and elongation of 1000%. The polymer displayed classic segmented thermoplastic elastomer morphology with distinct hard block and soft block phases. Thermal and dynamic mechanical analyses determined that the material has a useful service temperature range of around ?40 °C to +40 °C, making it an excellent candidate for low‐temperature elastomer and film applications, and potentially as a material for use in temporary orthopedic implant devices. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2990–3000, 2006     

Design considerations and coil comparisons for 7 T brain imaging

The development of 300 MHz radio-frequency (RF) head coils analogous to those used at field strengths of 1.5 and 3 T is complicated by increased dissipative losses in conductive tissue, effects arising from the short RF wavelength in biological tissue (about 13 cm at 300 MHz), and the constraints imposed by the use of head gradient sets desirable for mitigating increased static field susceptibility effects. In this study, five RF head coils were constructed and tested on a 7 T scanner including 2 TEM designs, 2 birdcage designs and a local receive-only array. Signal-to-noise ratio, coil reception profiles and interactions between the coil and dielectric head were examined. Particular attention was placed on the coil’s reception in the neck and shoulders, where the head gradient is unable to spatially encode the image. With the use of conductive shields and distributed capacitance, all of the coil designs could be made to image effectively at high field, but each design was found to have subtle differences in field distribution, interaction with the dielectric boundary conditions of the head and fringe fields in the neck and shoulders. In particular, the birdcage and array coils were found to have reducedB ₁ reception field profiles in the neck and shoulders which helped reduce signal detection outside the linear region of the head gradient coil. Although the TEM coils exhibited higher signal detection in the neck and shoulders, all the coils picked up enough signal from these regions to produce artifacts in the brain. These artifacts could be mitigated through use of a conductive shield or by small local dephasing shims sewn into the shoulders of a jacket worn by the subject. Although homogeneous in low-dielectric-constant phantoms, the volume coil’sB ₁ profile was strongly peaked in the center of the head, rendering them spatially complementary to that observed in the surface coil array. The image profile of the surface coil was found to be less dramatically changed from patterns observed at lower field strength. Its dielectric brightening pattern was found to depend on the orientation of the coil with respect to the head.     

Synthesis and characterisation of silica encapsulated cobalt nanoparticles and nanoparticle chains

Nanoparticles of cobalt were produced by direct reduction in aqueous solution. These were subsequently coated in silica by a very slow hydrolysis reaction. Electrostatic and magnetic forces between the nanoparticles led to ordered structures forming, which were analysed by high resolution transmission electron microscopy. SQUID magnetometry showed that the nanoparticles were ferromagnetic with an additional magnetic signal from highly disordered surface states. Off-axis electron holography of the structures was undertaken and gives evidence for the mechanism by which the structures form.     

Experimental calibration and field investigation of the oxygen isotopic fractionation between biogenic aragonite and water

Marine molluscs have long been recognised as potential records of palaeoclimate change using the patterns and differences in the stable isotopic composition of the carbonate shells. The aim of this study is to improve the robustness of this approach for aragonitic molluscs by completing the first experimental calibration of the fractionation between water and biogenic aragonite. Fractionation factors were calibrated by growing specimens of the freshwater mollusc Lymnaea peregra under controlled conditions of water temperature and isotopic composition. Fifteen populations of L. peregra were maintained at constant temperature and isotopic conditions for five months (at five different temperatures and using three different water compositions). Water samples and temperature measurements were taken regularly throughout the experiment. The temperature dependence of the fractionation factor, between 8 and 24 degrees C, is given by: 1000 ln alpha=16.74x(1000T(-1))-26.39 (T in Kelvin) and the relationship between temperature (T), delta(18)O(carb) and delta(18)O(wat) is given by: T=21.36-4.83xdelta(+ degrees )O(carb)-delta(+ degrees )O(wat) (T is in degrees C, delta(18)O(carb) is with respect to Vienna Pee Dee Belemnite (PDB), the International Atomic Energy Agency (IAEA) replacement standard for PDB, and delta(18)O(wat) is with respect to Vienna standard mean ocean water (VSMOW)) The outcome of the controlled experiment is compared with previous studies on synthetic, and biogenic, calcite and aragonite from field and laboratory investigations. These comparisons suggest that although a vital offset exists between the fractionation of isotopes in synthetic and biogenic aragonite for molluscs in general, there is no vital effect that is specific either to freshwater, or to individual, genera. Therefore, the calibrated relationship may be used for any freshwater or marine mollusc to derive palaeotemperatures providing the isotopic composition of the environmental water can be reliably constrained. Copyright 1999 John Wiley & Sons, Ltd.     

Dynamics of phase transitions induced by femtosecond laser pulse irradiation of indium phosphide

The structural transformation dynamics of single-crystalline indium phosphide (InP) irradiated with 150 fs laser pulses at 800 nm has been investigated by means of time-resolved reflectivity measurements covering a time window from 150 fs up to 500 ns. The results obtained show that for fluences above a threshold of 0.16 J/cm² thermal melting of the material occurs on the timescale of 1–2 ps. The evolution of the reflectivity on a longer timescale reveals the reflectivity of the liquid phase and shows resolidification times typically around 10–30 ns after which an amorphous layer several tens of nanometers thick is formed on the surface. This amorphous layer significantly alters the optical properties of the surface and finally leads to a reduced ablation threshold for subsequent laser pulses. Single-pulse ablation at higher fluences (>0.23 J/cm²) is preceded by an ultrafast phase transition (non-thermal melting) occurring within 400 fs after the arrival of the pulse to the surface. PACS 79.20.Ds; 78.47.+p; 64.70.-p     

Effect of paramagnetic anions on cations possessing stereochemically non-equivalent methylene groups

A series of cations based on substituted pyrrolidines and piperidines has been investigated by NMR in low dielectric solvents. Non-equivalent cation methylene protons are selectively shifted by paramagnetic anions; the size of the shift depends directly on the ability of the anion to approach closely the group in question. The assignments resulting from the shift data have been compared with the work of other authors.