Artificial construction of the layered Ruddlesden-Popper manganite La2Sr2Mn3O10 by reflection high energy electron diffraction monitored pulsed laser deposition

Pulsed laser deposition has been used to artificially construct the n = 3 Ruddlesden-Popper structure La(2)Sr(2)Mn(3)O(10) in epitaxial thin film form by sequentially layering La(1-x)Sr(x)MnO(3) and SrO unit cells aided by in situ reflection high energy electron diffraction monitoring. The interval deposition technique was used to promote two-dimensional SrO growth. X-ray diffraction and cross-sectional transmission electron microscopy indicated that the trilayer structure had been formed. A site ordering was found to differ from that expected thermodynamically, with the smaller Sr(2+) predominantly on the R site due to kinetic trapping of the deposited cation sequence. A dependence of the out-of-plane lattice parameter on growth pressure was interpreted as changing the oxygen content of the films. Magnetic and transport measurements on fully oxygenated films indicated a frustrated magnetic ground state characterized as a spin glass-like magnetic phase with the glass temperature T(g) ≈ 34 K. The magnetic frustration has a clear in-plane (ab) magnetic anisotropy, which is maintained up to temperatures of 150 K. Density functional theory calculations suggest competing antiferromagnetic and ferromagnetic long-range orders, which are proposed as the origin of the low-temperature glassy state.     

Removal of fission products from mixed solvents using zeolites

The solvents tributylphosphate (TBP) and odourless kerosene (OK) are widely used to extract plutonium(IV) and uranium(V) in nuclear processing plants. Although these solvents are chosen because of their low affinity for fission products it is, nevertheless, of value to study ways of removing the small quantities of fission products, such as isotopes of Cs, Sr and Ru, which can be present in the solvents. This paper describes simple distribution coefficients (K _d) measurements made to test the ability of the aluminosilicate zeolites to remove¹⁰⁶Ru from TBP, OK, and their mixtures.     

Photoproducts Formed in the Photoyellowing of Collagen in the Presence of a Fluorescent Whitening Agent

Fibrous proteins discolor on exposure to the UV component of sunlight. This effect is exacerbated in the presence of fluorescent whitening agents (FWAs), which are often applied to textiles to improve product brightness. Tryptophan photoproducts have been identified as significant contributors to protein photoyellowing; however, the role of non–tryptophan-derived chromophores is less clear. In this study bovine collagen, containing no tryptophan residues, was irradiated in the presence and absence of the stilbene-derived FWA, 4,4'-bis(2-sulfostyryl)biphenyl (DSBP) and photoproducts were identified using mass spectrometry. Photoyellowing was found to be dependent on the presence of the FWA, attributed to amplified generation of reactive oxygen species (ROS), particularly hydroxyl radicals and peroxynitrite. Four key proteinaceous photomodifications contributing directly to photoyellowing were located in irradiated collagen pretreated with DSBP, namely dopa, nitrophenylalanine, nitrotyrosine and nitrohistidine. This represents the first direct characterization of the three nitrated residues in the photoyellowing of an isolated fibrous protein, and implicates the ROS, peroxynitrite, as a key contributor to protein photoyellowing. Direct oxidative modification of the FWA itself was also observed. This study demonstrates that, even in the absence of tryptophan residues, significant photomodification of protein residues leading to chromophore formation occurs in the presence of an FWA.     

Photoinitiated polymerization of styrene from self‐assembled monolayers on gold. II. Grafting rates and extraction

Ultrathin films of polystyrene (PS) were grown from self‐assembled monolayers by the “grafting‐from” technique. The initiating system consisted of a dithiol azobisisobutyronitrile‐type free‐radical initiator that was activated by irradiation at 300 nm. The thickness of the PS films ranged from 7 to 190 nm and could be controlled by varying the reaction time or the monomer concentration. The films were characterized by ellipsometry and Fourier transform‐reflection absorption infrared spectroscopy after Soxhlet extraction of residual physisorbed polymer. These films were unstable above 60 °C, and a water‐jacketed Soxhlet extractor was designed to maintain solvent temperatures below 45 °C during extraction. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3284–3291, 2002     

Mass spectrometry imaging of triglycerides in biological tissues by laser desorption ionization from silicon nanopost arrays

Mass spectrometry imaging (MSI) is used increasingly to simultaneously detect a broad range of biomolecules while mapping their spatial distributions within biological tissue sections. Matrix‐assisted laser desorption ionization (MALDI) is recognized as the method‐of‐choice for MSI applications due in part to its broad molecular coverage. In spite of the remarkable advantages offered by MALDI, imaging of neutral lipids, such as triglycerides (TGs), from tissue has remained a significant challenge due to ion suppression of TGs by phospholipids, e.g. phosphatidylcholines (PCs). To help overcome this limitation, silicon nanopost array (NAPA) substrates were introduced to selectively ionize TGs from biological tissue sections. This matrix‐free laser desorption ionization (LDI) platform was previously shown to provide enhanced ionization of certain lipid classes, such as hexosylceramides (HexCers) and phosphatidylethanolamines (PEs) from mouse brain tissue. In this work, we present NAPA as an MSI platform offering enhanced ionization efficiency for TGs from biological tissues relative to MALDI, allowing it to serve as a complement to MALDI‐MSI. Analysis of a standard lipid mixture containing PC(18:1/18:1) and TG(16:0/16:0/16:0) by LDI from NAPA provided an ~49 and ~227‐fold higher signal for TG(16:0/16:0/16:0) relative to MALDI, when analyzed without and with the addition of a sodium acetate, respectively. In contrast, MALDI provided an ~757 and ~295‐fold higher signal for PC(18:1/18:1) compared with NAPA, without and with additional Na⁺. Averaged signal intensities for TGs from MSI of mouse lung and human skin tissues exhibited an ~105 and ~49‐fold increase, respectively, with LDI from NAPA compared with MALDI. With respect to PCs, MALDI provided an ~2 and ~19‐fold increase in signal intensity for mouse lung and human skin tissues, respectively, when compared with NAPA. The complementary coverage obtained by the two platforms demonstrates the utility of using both techniques to maximize the information obtained from lipid MS or MSI experiments.     

A multi-scale assessment of Pb(II) sorption on dolomite

Macroscopic sorption studies indicated that Pb sorption capacity was independent of pH over the pH range 5-7, while sorption as a function of reaction time up to two weeks for systems with no bulk precipitate phases showed continuous Pb uptake on dolomite. This could be due to diffusion of Pb into the micropores of dolomite as well as an increase in surface sites caused by particle size reduction during suspension mixing. Normalized XANES spectra for systems undersaturated with respect to Pb carbonate precipitates resembled the spectrum of Pb4(OH)4(4+), suggesting that Pb is mainly coordinated to dolomite as an inner-sphere surface complex. On the other hand, the XANES spectrum for 10(-3) M Pb at 1 atm CO2(g) in a 2 M Mg(NO3)2 background electrolyte solution resembled that of cerussite, while a sample at 5 x 10(-4) M Pb in equilibrium with air and 2 M Mg(NO3)2 resembled that of hydrocerussite. EXAFS analyses of sorption samples in chloride solutions showed that there were only first-shell contributions under 1 atm CO2(g), while higher shell contributions from Ca/Mg were seen at 10(-3.42) atm CO2(g). On the other hand, EXAFS samples prepared in nitrate solutions showed noticeable differences in speciation under different reaction conditions-from outer-sphere surface complexes at low Pb concentrations and pH, to inner-sphere surface complexes at moderate Pb concentrations and neutral pH, to the formation of Pb carbonate precipitates at the highest Pb loadings.