Effect of Pr-Ca substitution on the transport and magnetic behavior of LaMnO3 perovskite

The effect of simultaneous substitution of a fluctuating cation and a divalent cation in LaMnO₃ perovskite modifies the properties of the material to exhibit large valence colossal magnetoresistance (CMR) effect. A good example of these properties is (La_1−2x Pr _x Ca _x )MnO₃ (LPCMO) type CMR material. In this communication it is reported that, with the increase in x (for x=0.1, 0.15, 0.2), the T _c varies between 100 and 120 K with improvisation in metal-insulator transition. Interestingly, resistance increases with x from few hundred ohms to few kilo ohms with corresponding decrease in the unit cell volume. The results of the studies using X-ray diffraction (XRD), electrical resistivity, magnetoresistance and ac susceptibility measurements on LPCMO samples for understanding the structural, transport and magnetic properties are discussed in detail.     

Three-dimensional visualization of protein expression in mouse brain structures using imaging mass spectrometry

We have developed a method to visualize matrix-assisted laser desorption ionization imaging mass spectrometry (MALDI IMS) data aligned with optically determinable tissue structures in three dimensions. Details of the methodology are exemplified using the 3-D reconstruction of myelin basic protein (MBP) in the corpus callosum of a mouse brain. In this procedure, optical images obtained from serial coronal sections are first aligned to each other to reconstruct a surface of the corpus callosum from segmented contours of the aligned images. The MALDI IMS data are then coregistered to the optical images and superimposed into the surface to create the final 3-D visualization. Correlating proteomic data with anatomical structures provides a more comprehensive understanding of healthy and pathological brain functions, and holds promise to be utilized in more complex anatomical arrangements.     

Thioflavin T hydroxylation at basic pH and its effect on amyloid fibril detection

The fluorescent dye thioflavin T (ThT) is commonly used for in situ amyloid fibril detection. In this work, we focused on the spectroscopic properties and chemical stability of ThT in aqueous solution as a function of pH, temperature, and dye concentration. A reversible hydroxylation process occurs in alkaline solutions, which was characterized using a combination of UV-vis absorption spectroscopy, proton NMR, and density functional theory (DFT). On the basis of these studies, we propose a chemical structure for the hydroxylated form. Finally, by means of fluorescence spectroscopy, ThT hydroxylation effects on in situ amyloid detection have been investigated, providing new insights on the efficiency of the ThT assay for quantitative fibril evaluation at basic pH.     

Speciation measurements of uranium in alkaline waters using diffusive gradients in thin films technique

This work investigated the application of diffusive gradients in thin films technique (DGT) to uranium speciation measurements in natural water. Two binding phases were examined, a commercially available affinity membrane, Whatman DE 81 (DE 81), with amino binding functional groups and the conventionally used Chelex 100 beads imbedded polyacrylamide hydrogel (Chelex) with iminodiacetate functional groups. The DGT devices assembled with the binding phases of DE 81 (DE 81 DGT) and Chelex gel (Chelex DGT) were tested both in synthetic river water solutions and in local river water. DE 81 DGT and Chelex DGT measured 80% and 75% of the total uranium in synthetic river water solution, respectively, and measured 73% and 60% of the total uranium in St. Lawrence River, Canada, respectively. The binding properties of the DE 81 membrane and Chelex gel for uranium, and the diffusion of uranyl complexes in the polyacrylamide gel (PAM) were also studied.     

Condensation reaction in the bandpass reaction cell improves sensitivity for uranium,thorium, neodymium and praseodymium measurements

Condensation reactions in the bandpass reaction cell or dynamic reaction cell (DRC) were used for the determination of actinides and lanthanides such as uranium, thorium, neodymium and praseodymium. These elements react with oxygen reagent gas in the dynamic reaction cell of the ELAN DRC II instrument to give mono- and/or dioxo cationic species (UO₂⁺, ThO⁺, NdO⁺ and PrO⁺, respectively). Increasing the oxygen flow rate in the dynamic reaction cell leads to the rapid decrease of the singly charged metal ions accompanied by the fast increase in the intensity of the oxide ion. This phenomenon is used to improve considerably the sensitivity of ICP-MS instruments equipped with a dynamic reaction cell for actinides and lanthanides. Estimated detection limits (EDL) obtained in this work for uranium, thorium, neodymium-144 and praseodymium are 0.022, 1.0, 0.045, and 0.10 ng L^–1, respectively. The detection limit for uranium measured in the standard (vented) mode of an ELAN DRC II was found to be 0.22 ng L^–1, which is an order of magnitude higher compared to the pressurized mode.     

Conformations of laulimalide in DMSO-d6

Laulimalide is one of the newest naturally occurring macrolides known to act as a microtubule stabilizing agent with properties similar to Taxol. It also stands as being one of the most flexible with 18 rotatable bonds. This large number of rotatable bonds allows for approximately 3(18) potential conformers. To examine the conformational energy surface of laulimalide, we have performed an NAMFIS deconvolution analysis for laulimalide in DMSO-d6. The latter has been supplemented with a post-NAMFIS energy analysis at the Becke3LYP/6-31G level that examines the opposing effects of internal hydrogen bonding and syn-pentane interactions. In this way, we have identified 15 laulimalide conformations that can be classified into 5 different families: Supine, Convex, Cobra, Stretch, and Concave motifs.     

Combination of LC-ICP-MS, LC-MS and NMR for investigation of the oxidative degradation of selenomethionine

Selenomethionine (SeMet) was oxidized by heating an acidic solution with hydrogen peroxide. Samples were taken before and during the oxidation process. The oxidation products were separated by cation exchange chromatography followed by ICP-MS detection to identify the selenium containing compounds as well as electrospray ionization MS detection to determine the masses of the degradation products. Furthermore, the samples were analyzed by ⁷⁷Se-NMR. The first appearing degradation product was selenomethionine selenoxide, which was converted via the deaminated selenoxide to methane seleninic acid and selenite.     

Processing MALDI Mass Spectra to Improve Mass Spectral Direct Tissue Analysis

Profiling and imaging biological specimens using MALDI mass spectrometry has significant potential to contribute to our understanding and diagnosis of disease. The technique is efficient and high-throughput providing a wealth of data about the biological state of the sample from a very simple and direct experiment. However, in order for these techniques to be put to use for clinical purposes, the approaches used to process and analyze the data must improve. This study examines some of the existing tools to baseline subtract, normalize, align, and remove spectral noise for MALDI data, comparing the advantages of each. A preferred workflow is presented that can be easily implemented for data in ASCII format. The advantages of using such an approach are discussed for both molecular profiling and imaging mass spectrometry.     

Rapid dissolution of large environmental samples for the determination of fission products

The dissolution of large environmental samples was investigated using a microwave autoclave, capable of digestion conditions of 300 °C and 200 bar, for the application of rapid determination of radionuclides. Six samples of up to 5 g plant material were digested, also eliminating predigestion steps such as ashing and grinding. Batches of forty 1 g samples of plant leaves were also completely digested in 75 minutes. Quantitative recovery of ⁹⁰Sr from 5 g soil samples by leaching with 8M HNO₃ at 200 °C was achieved, whereas ¹³⁷Cs was not completely recovered from the large soil samples using total digestion or leaching (HCl:HNO₃) techniques, but quantitative recovery was achieved using fusion and sinter procedures.