Motion of the plasma critical layer during relativistic-electron laser interaction with immobile and comoving ion plasma for ion accelerationa)

NASA Astrophysics Data System (ADS)

Sahai, Aakash A.

2014-05-01

We analyze the motion of the plasma critical layer by two different processes in the relativistic-electron laser-plasma interaction regime (a0>1). The differences are highlighted when the critical layer ions are stationary in contrast to when they move with it. Controlling the speed of the plasma critical layer in this regime is essential for creating low-β traveling acceleration structures of sufficient laser-excited potential for laser ion accelerators. In Relativistically Induced Transparency Acceleration (RITA) scheme, the heavy plasma-ions are fixed and only trace-density light-ions are accelerated. The relativistic critical layer and the acceleration structure move longitudinally forward by laser inducing transparency through apparent relativistic increase in electron mass. In the Radiation Pressure Acceleration (RPA) scheme, the whole plasma is longitudinally pushed forward under the action of the laser radiation pressure, possible only when plasma ions co-propagate with the laser front. In RPA, the acceleration structure velocity critically depends upon plasma-ion mass in addition to the laser intensity and plasma density. In RITA, mass of the heavy immobile plasma-ions does not affect the speed of the critical layer. Inertia of the bared immobile ions in RITA excites the charge separation potential, whereas RPA is not possible when ions are stationary.

Anisotropic expansion and amorphization of Ga2O3 irradiated with 946 MeV Au ions

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Lang, Maik; Severin, Daniel; Bender, Markus; Trautmann, Christina; Ewing, Rodney C.

2016-05-01

The structural response of β-Ga2O3 to irradiation-induced electronic excitation was investigated. A polycrystalline pellet of this material was irradiated with 946 MeV Au ions and the resulting structural modifications were characterized using in situ X-ray diffraction analysis at various ion fluences, up to 1 × 1013 cm-2. Amorphization was induced, with the accumulation of the amorphous phase following a single-impact mechanism in which each ion produces an amorphous ion track along its path. Concurrent with this phase transformation, an increase in the unit cell volume of the material was observed and quantified using Rietveld refinement. This unit cell expansion increased as a function of ion fluence before saturating at 1.8%. This effect is attributed to the generation of defects in an ion track shell region surrounding the amorphous track cores. The unit cell parameter increase was highly anisotropic, with no observed expansion in the [0 1 0] direction. This may be due to the structure of β-Ga2O3, which exhibits empty channels of connected interstitial sites oriented in this direction.

Focused-ion-beam induced interfacial intermixing of magnetic bilayers for nanoscale control of magnetic properties.

PubMed

Burn, D M; Hase, T P A; Atkinson, D

2014-06-11

Modification of the magnetic properties in a thin-film ferromagnetic/non-magnetic bilayer system by low-dose focused ion-beam (FIB) induced intermixing is demonstrated. The highly localized capability of FIB may be used to locally control magnetic behaviour at the nanoscale. The magnetic, electronic and structural properties of NiFe/Au bilayers were investigated as a function of the interfacial structure that was actively modified using focused Ga(+) ion irradiation. Experimental work used MOKE, SQUID, XMCD as well as magnetoresistance measurements to determine the magnetic behavior and grazing incidence x-ray reflectivity to elucidate the interfacial structure. Interfacial intermixing, induced by low-dose irradiation, is shown to lead to complex changes in the magnetic behavior that are associated with monotonic structural evolution of the interface. This behavior may be explained by changes in the local atomic environment within the interface region resulting in a combination of processes including the loss of moment on Ni and Fe, an induced moment on Au and modifications to the spin-orbit coupling between Au and NiFe.

120 MeV Ni Ion beam induced modifications in poly (ethylene terephthalate) used in commercial bottled water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Vijay; Sonkawade, R. G.; Ali, Yasir

2012-06-05

We report the effects of heavy ion irradiation on the optical, structural, and chemical properties of polyethylene terephthalate (PET) film used in commercial bottled water. PET bottles were exposed with 120 MeV Ni ions at fluences varying from 3 x 10{sup 10} to 3 x 10{sup 12} ion/cm{sup 2}. The modifications so induced were analyzed by using UV-Vis, X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy. Substantial decrease in optical band gap is observed with the increase in ion fluence. In the FTIR spectra, most of bands are decreased due the degradation of the molecular structure. XRD measurements showmore » the decrease in peak intensity, which reflects the loss of crystallinity after irradiation.« less

Changes in Phosphatidylcholine Headgroup Tilt and Water Order Induced by Monovalent Salts: Molecular Dynamics Simulations

PubMed Central

Sachs, Jonathan N.; Nanda, Hirsh; Petrache, Horia I.; Woolf, Thomas B.

2004-01-01

The association between monovalent salts and neutral lipid bilayers is known to influence global bilayer structural properties such as headgroup conformational fluctuations and the dipole potential. The local influence of the ions, however, has been unknown due to limited structural resolution of experimental methods. Molecular dynamics simulations are used here to elucidate local structural rearrangements upon association of a series of monovalent Na+ salts to a palmitoyl-oleoyl-phosphatidylcholine bilayer. We observe association of all ion types in the interfacial region. Larger anions, which are meant to rationalize data regarding a Hofmeister series of anions, bind more deeply within the bilayer than either Cl− or Na+. Although the simulations are able to reproduce experimentally measured quantities, the analysis is focused on local properties currently invisible to experiments, which may be critical to biological systems. As such, for all ion types, including Cl−, we show local ion-induced perturbations to headgroup tilt, the extent and direction of which is sensitive to ion charge and size. Additionally, we report salt-induced ordering of the water well beyond the interfacial region, which may be significant in terms of hydration repulsion between stacked bilayers. PMID:15189873

Single ion induced surface nanostructures: a comparison between slow highly charged and swift heavy ions.

PubMed

Aumayr, Friedrich; Facsko, Stefan; El-Said, Ayman S; Trautmann, Christina; Schleberger, Marika

2011-10-05

This topical review focuses on recent advances in the understanding of the formation of surface nanostructures, an intriguing phenomenon in ion-surface interaction due to the impact of individual ions. In many solid targets, swift heavy ions produce narrow cylindrical tracks accompanied by the formation of a surface nanostructure. More recently, a similar nanometric surface effect has been revealed for the impact of individual, very slow but highly charged ions. While swift ions transfer their large kinetic energy to the target via ionization and electronic excitation processes (electronic stopping), slow highly charged ions produce surface structures due to potential energy deposited at the top surface layers. Despite the differences in primary excitation, the similarity between the nanostructures is striking and strongly points to a common mechanism related to the energy transfer from the electronic to the lattice system of the target. A comparison of surface structures induced by swift heavy ions and slow highly charged ions provides a valuable insight to better understand the formation mechanisms. © 2011 IOP Publishing Ltd

Cross-sectional transmission electron microscopic study of irradiation induced nano-crystallization of nickel in a W/Ni multilayer.

PubMed

Bagchi, Sharmistha; Lalla, N P

2008-06-11

The present study reports the cross-sectional transmission electron microscopic investigations of swift heavy ion-irradiation induced nano-size recrystallization of Ni in a nearly immiscible W/Ni multilayer structure. Multilayer structures (MLS) of [W(25 Å)/Ni(25 Å)](10BL) were grown on Si-(100) substrate by the ion-beam sputtering technique. The as-synthesized MLS were subjected to 120 MeV-Au(9+) ion-irradiation to a fluence of ∼5 × 10(13) ions cm(-2). Wide-angle x-ray diffraction studies of pristine as well as irradiated W/Ni multilayers show deterioration of the superlattice structure, whereas x-ray reflectivity (XRR) measurement reveals a nearly unaffected microstructure after irradiation. Analysis of the XRR data using 'Parratt's formalism' does show a significant increase of W/Ni interface roughness. Cross-sectional transmission electron microscopy (TEM) studies carried out in diffraction and imaging modes (including bright-field and dark-field imaging), show that at high irradiation dose the intralayer microstructure of Ni becomes nano-crystalline (1-2 nm). During these irradiation induced changes of the intralayer microstructure, the interlayer definition of the W and Ni layers still remains intact. The observed nano-recrystallization of Ni has been attributed to competition between low miscibility of the W/Ni interface and the ion-beam induced mixing kinetics.

Positive Ion Induced Solidification of He4

NASA Astrophysics Data System (ADS)

Moroshkin, P.; Lebedev, V.; Weis, A.

2009-03-01

We have observed bulk solidification of He4 induced by nucleation on positive alkali ions in pressurized superfluid helium. The ions are extracted into the liquid from alkali-doped solid He by a static electric field. The experiments prove the existence of charged particles in a solid structure composed of doped He that was recently shown to coexist with superfluid helium below the He solidification pressure. This supports our earlier suggestion that the Coulomb interaction of positive ions surrounded by a solid He shell (snowballs) and electrons trapped in spherical cavities (electron bubbles), together with surface tension, is responsible for the stability of that structure against melting. We have determined the density of charges in the sample by two independent methods.

The influence of projectile ion induced chemistry on surface pattern formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karmakar, Prasanta, E-mail: prasantak@vecc.gov.in; Satpati, Biswarup

We report the critical role of projectile induced chemical inhomogeneity on surface nanostructure formation. Experimental inconsistency is common for low energy ion beam induced nanostructure formation in the presence of uncontrolled and complex contamination. To explore the precise role of contamination on such structure formation during low energy ion bombardment, a simple and clean experimental study is performed by selecting mono-element semiconductors as the target and chemically inert or reactive ion beams as the projectile as well as the source of controlled contamination. It is shown by Atomic Force Microscopy, Cross-sectional Transmission Electron Microscopy, and Electron Energy Loss Spectroscopy measurementsmore » that bombardment of nitrogen-like reactive ions on Silicon and Germanium surfaces forms a chemical compound at impact zones. Continuous bombardment of the same ions generates surface instability due to unequal sputtering and non-uniform re-arrangement of the elemental atom and compound. This instability leads to ripple formation during ion bombardment. For Argon-like chemically inert ion bombardment, the chemical inhomogeneity induced boost is absent; as a result, no ripples are observed in the same ion energy and fluence.« less

Linkage Determination of Linear Oligosaccharides by MSn (n > 2) Collision-Induced Dissociation of Z1 Ions in the Negative Ion Mode

NASA Astrophysics Data System (ADS)

Konda, Chiharu; Bendiak, Brad; Xia, Yu

2014-02-01

Obtaining unambiguous linkage information between sugars in oligosaccharides is an important step in their detailed structural analysis. An approach is described that provides greater confidence in linkage determination for linear oligosaccharides based on multiple-stage tandem mass spectrometry (MSn, n >2) and collision-induced dissociation (CID) of Z1 ions in the negative ion mode. Under low energy CID conditions, disaccharides 18O-labeled on the reducing carbonyl group gave rise to Z1 product ions (m/z 163) derived from the reducing sugar, which could be mass-discriminated from other possible structural isomers having m/z 161. MS3 CID of these m/z 163 ions showed distinct fragmentation fingerprints corresponding to the linkage types and largely unaffected by sugar unit identities or their anomeric configurations. This unique property allowed standard CID spectra of Z1 ions to be generated from a small set of disaccharide samples that were representative of many other possible isomeric structures. With the use of MSn CID (n = 3 - 5), model linear oligosaccharides were dissociated into overlapping disaccharide structures, which were subsequently fragmented to form their corresponding Z1 ions. CID data of these Z1 ions were collected and compared with the standard database of Z1 ion CID using spectra similarity scores for linkage determination. As the proof-of-principle tests demonstrated, we achieved correct determination of individual linkage types along with their locations within two trisaccharides and a pentasaccharide.

Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ligare, Marshall R.; Baker, Erin S.; Laskin, Julia

Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

Motion of the plasma critical layer during relativistic-electron laser interaction with immobile and comoving ion plasma for ion acceleration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sahai, Aakash A., E-mail: aakash.sahai@gmail.com

2014-05-15

We analyze the motion of the plasma critical layer by two different processes in the relativistic-electron laser-plasma interaction regime (a{sub 0}>1). The differences are highlighted when the critical layer ions are stationary in contrast to when they move with it. Controlling the speed of the plasma critical layer in this regime is essential for creating low-β traveling acceleration structures of sufficient laser-excited potential for laser ion accelerators. In Relativistically Induced Transparency Acceleration (RITA) scheme, the heavy plasma-ions are fixed and only trace-density light-ions are accelerated. The relativistic critical layer and the acceleration structure move longitudinally forward by laser inducing transparencymore » through apparent relativistic increase in electron mass. In the Radiation Pressure Acceleration (RPA) scheme, the whole plasma is longitudinally pushed forward under the action of the laser radiation pressure, possible only when plasma ions co-propagate with the laser front. In RPA, the acceleration structure velocity critically depends upon plasma-ion mass in addition to the laser intensity and plasma density. In RITA, mass of the heavy immobile plasma-ions does not affect the speed of the critical layer. Inertia of the bared immobile ions in RITA excites the charge separation potential, whereas RPA is not possible when ions are stationary.« less

Radiation-induced disorder in compressed lanthanide zirconates.

PubMed

Park, Sulgiye; Tracy, Cameron L; Zhang, Fuxiang; Park, Changyong; Trautmann, Christina; Tkachev, Sergey N; Lang, Maik; Mao, Wendy L; Ewing, Rodney C

2018-02-28

The effects of swift heavy ion irradiation-induced disordering on the behavior of lanthanide zirconate compounds (Ln 2 Zr 2 O 7 where Ln = Sm, Er, or Nd) at high pressures are investigated. After irradiation with 2.2 GeV 197 Au ions, the initial ordered pyrochlore structure (Fd3[combining macron]m) transformed to a defect-fluorite structure (Fm3[combining macron]m) in Sm 2 Zr 2 O 7 and Nd 2 Zr 2 O 7 . For irradiated Er 2 Zr 2 O 7 , which has a defect-fluorite structure, ion irradiation induces local disordering by introducing Frenkel defects despite retention of the initial structure. When subjected to high pressures (>29 GPa) in the absence of irradiation, all of these compounds transform to a cotunnite-like (Pnma) phase, followed by sluggish amorphization with further compression. However, if these compounds are irradiated prior to compression, the high pressure cotunnite-like phase is not formed. Rather, they transform directly from their post-irradiation defect-fluorite structure to an amorphous structure upon compression (>25 GPa). Defects and disordering induced by swift heavy ion irradiation alter the transformation pathways by raising the energetic barriers for the transformation to the high pressure cotunnite-like phase, rendering it inaccessible. As a result, the high pressure stability field of the amorphous phase is expanded to lower pressures when irradiation is coupled with compression. The responses of materials in the lanthanide zirconate system to irradiation and compression, both individually and in tandem, are strongly influenced by the specific lanthanide composition, which governs the defect energetics at extreme conditions.

Effects of urea induced protein conformational changes on ion exchange chromatographic behavior.

PubMed

Hou, Ying; Hansen, Thomas B; Staby, Arne; Cramer, Steven M

2010-11-19

Urea is widely employed to facilitate protein separations in ion exchange chromatography at various scales. In this work, five model proteins were used to examine the chromatographic effects of protein conformational changes induced by urea in ion exchange chromatography. Linear gradient experiments were carried out at various urea concentrations and the protein secondary and tertiary structures were evaluated by far UV CD and fluorescence measurements, respectively. The results indicated that chromatographic retention times were well correlated with structural changes and that they were more sensitive to tertiary structural change. Steric Mass Action (SMA) isotherm parameters were also examined and the results indicated that urea induced protein conformational changes could affect both the characteristic charge and equilibrium constants in these systems. Dynamic light scattering analysis of changes in protein size due to urea-induced unfolding indicated that the size of the protein was not correlated with SMA parameter changes. These results indicate that while urea-induced structural changes can have a marked effect on protein chromatographic behavior in IEX, this behavior can be quite complicated and protein specific. These differences in protein behavior may provide insight into how these partially unfolded proteins are interacting with the resin material. Copyright © 2010 Elsevier B.V. All rights reserved.

Identification of Isomeric N-Glycan Structures by Mass Spectrometry with 157 nm Laser-Induced Photofragmentation

PubMed Central

Devakumar, Arugadoss; Mechref, Yehia; Kang, Pilsoo; Novotny, Milos V.; Reilly, James P.

2008-01-01

Characterization of structural isomers has become increasingly important and extremely challenging in glycobiology. This communication demonstrates the capability of ion-trap mass spectrometry in conjunction with 157 nm photofragmentation to identify different structural isomers of permethylated N-glycans derived from ovalbumin without chromatographic separation. The results are compared with CID experiments. Photodissociation generates extensive cross-ring fragment ions as well as diagnostic glycosidic product ions that are not usually observed in CID MS/MS experiments. The detection of these product ions aids in characterizing indigenous glycan isomers. The ion-trap facilitates MSn experiments on the diagnostic glycosidic fragments and cross-ring product ions generated through photofragmentation, thus allowing unambiguous assignment of all of the isomeric structures associated with the model glycoprotein utilized in this study. Photofragmentation is demonstrated to be a powerful technique for the structural characterization of glycans. PMID:18487060

Effect of structure and thermodynamic stability on the response of lanthanide stannate pyrochlores to ion beam irradiation.

PubMed

Lian, J; Helean, K B; Kennedy, B J; Wang, L M; Navrotsky, A; Ewing, R C

2006-02-09

The lanthanide stannates, Ln2Sn2O7, Ln=La-Lu and Y, have the isometric pyrochlore structure, A2B2O7, and their structural properties have been refined by Rietveld analysis of powder neutron and synchrotron X-ray diffraction data. In this study, the enthalpies of formation of selected stannate pyrochlores, Ln=La, Nd, Sm, Eu, Dy, and Yb, were measured by high-temperature oxide melt solution calorimetry. Their radiation response was determined by 1 MeV Kr2+ ion irradiation combined with in situ TEM observation over the temperature range of 25 to 1000 K. The enthalpy of formation from binary oxides of stannate pyrochlores became more endothermic (from -145 to -40 kJ/mol) as the size of the lanthanide in the A-site decreases. A more exothermic trend of the enthalpy of formation was observed in stannate pyrochlores with larger lanthanide ions, particularly La, possibly as a result of increased covalency in the Sn-O bond. In contrast to lanthanide titanate pyrochlores, Ln2Ti2O7, that are generally susceptible to radiation-induced amorphization and zirconate pyrochlores, Ln2Zr2O7, that are generally resistant to radiation-induced amorphization, the lanthanide stannate pyrochlores show a much greater variation in their response to ion irradiation. La, Nd, and Gd stannates experience the radiation-induced transformation to the aperiodic state, and the critical amorphization temperatures are approximately 960, 700, and 350 K, respectively. Y and Er stannate pyrochlores cannot be amorphized by ion beam irradiation, even at 25 K, and instead disorder to a defect fluorite structure. Comparison of the calorimetric and ion irradiation data for titanate, zirconate, and stannate pyrochlores reveals a strong correlation among subtle changes in crystal structure with changing composition, the energetics of the disordering process, and the temperature above which the material can no longer be amorphized. In summary, as the structure approaches the ideal, ordered pyrochlore structure, radiation-induced amorphization is more easily attained. This is consistent with an increasingly exothermic trend in the enthalpies of formation of pyrochlores from the oxides, that is, the greater the thermochemical stability of the pyrochlore structure, the more likely it will be amorphized upon radiation damage rather than recover to a disordered fluorite structure.

Local atomic and electronic structure of oxide/GaAs and SiO2/Si interfaces using high-resolution XPS

NASA Technical Reports Server (NTRS)

Grunthaner, F. J.; Grunthaner, P. J.; Vasquez, R. P.; Lewis, B. F.; Maserjian, J.; Madhukar, A.

1979-01-01

The chemical structures of thin SiO2 films, thin native oxides of GaAs (20-30 A), and the respective oxide-semiconductor interfaces, have been investigated using high-resolution X-ray photoelectron spectroscopy. Depth profiles of these structures have been obtained using argon ion bombardment and wet chemical etching techniques. The chemical destruction induced by the ion profiling method is shown by direct comparison of these methods for identical samples. Fourier transform data-reduction methods based on linear prediction with maximum entropy constraints are used to analyze the discrete structure in oxides and substrates. This discrete structure is interpreted by means of a structure-induced charge-transfer model.

3D chiral and 2D achiral cobalt(ii) compounds constructed from a 4-(benzimidazole-1-yl)benzoic ligand exhibiting field-induced single-ion-magnet-type slow magnetic relaxation.

PubMed

Wang, Yu-Ling; Chen, Lin; Liu, Cai-Ming; Du, Zi-Yi; Chen, Li-Li; Liu, Qing-Yan

2016-05-04

Organizing magnetically isolated 3d transition metal ions, which behave as single-ion magnet (SIM) units, in a coordination network is a promising approach to design novel single-molecule magnets (SMMs). Herein 3D chiral and 2D achiral cobalt(ii) coordination compounds based on single metal nodes with a 4-(benzimidazole-1-yl)benzoic acid (Hbmzbc) ligand, namely, [Co(bmzbc)2(1,2-etdio)]n () (1,2-etdio = 1,2-ethanediol) and [Co(bmzbc)2(Hbmzbc)]n (), have been synthesized and structurally characterized. The 3D chiral structure with 2-fold interpenetrating qtz topological nets consisting of totally achiral components was obtained via spontaneous resolution, while the achiral structure is a 2D (4,4) net. In both structures, individual cobalt(ii) ions are spatially well separated by the long organic ligands in the well-defined networks. Magnetic measurements on and showed field-induced slow magnetic relaxation resulting from single-ion anisotropy of the individual Co(ii) ions. Analysis of the dynamic ac susceptibilities with the Arrhenius law afforded an anisotropy energy barrier of 16.8(3) and 31.3(2) K under a 2 kOe static magnetic field for and , respectively. The distinct coordination environments of the Co(ii) ions in and lead to the different anisotropic energy barriers.

Influence of Ar-ion implantation on the structural and mechanical properties of zirconia as studied by Raman spectroscopy and nanoindentation techniques

NASA Astrophysics Data System (ADS)

Kurpaska, L.; Jasinski, J.; Wyszkowska, E.; Nowakowska-Langier, K.; Sitarz, M.

2018-04-01

In this study, structural and nanomechanical properties of zirconia polymorphs induced by ion irradiation were investigated by means of Raman spectroscopy and nanoindentation techniques. The zirconia layer have been produced by high temperature oxidation of pure zirconium at 600 °C for 5 h at normal atmospheric pressure. In order to distinguish between the internal and external parts of zirconia, the spherical metallographic sections have been prepared. The samples were irradiated at room temperature with 150 keV Ar+ ions at fluences ranging from 1 × 1015 to 1 × 1017 ions/cm2. The main objective of this study was to distinguish and confirm different structural and mechanical properties between the interface layer and fully developed scale in the internal/external part of the oxide. Conducted studies suggest that increasing ion fluence impacts Raman bands positions (especially characteristic for tetragonal phase) and increases the nanohardness and Young's modulus of individual phases. This phenomenon has been examined from the point of view of stress-induced hardening effect and classical monoclinic → tetragonal (m → t) martensitic phase transformation.

Collision-induced dissociation of aminophospholipids (PE, MMPE, DMPE, PS): an apparently known fragmentation process revisited.

PubMed

Pittenauer, Ernst; Rehulka, Pavel; Winkler, Wolfgang; Allmaier, Günter

2015-07-01

A new type of low-mass substituted 4-oxazolin product ions of [M + H](+) precursor ions of aminophospholipids (glycerophosphatidylethanolamine, glycerophosphatidyl-N-methylethanolamine, glycerophosphatidyl-N,N-dimethylethanolamine, glycerophosphatidylserine) resulting from high-energy collision-induced dissociation (matrix-assisted laser desorption/ionization time-of-flight/reflectron time-of-flight mass spectrometry) and low-energy collision-induced dissociation (e.g., electrospray ionization quadrupole reflectron time-of-flight mass spectrometry) with accurate mass determination is described; these were previously misidentified as CHO-containing radical cationic product ions. The mechanism for the formation of these ions is proposed to be via rapid loss of water followed by cyclization to an 11-membered-ring transition state for the sn-1 fatty acid substituent and to a ten-membered-ring transition state for the sn-2 fatty acid substituent, and via final loss of monoacylglycerol phosphate, leading to substituted 4-oxazolin product ions. The minimum structural requirement for this interesting skeletal rearrangement fragmentation is an amino group linked to at least one hydrogen atom (i.e., ethanolamine, N-methylethanolamine, serine). Therefore, N,N-dimethylethanolamine derivates do not exhibit this type of fragmentation. The analytical value of these product ions is given by the fact that by post source decay and particularly high-energy collision-induced dissociation achieved via matrix-assisted laser desorption/ionization time-of-flight/reflectron time-of-flight mass spectrometry, the sn-2-related substituted 4-oxazolin product ion is always significantly more abundant than the sn-1-related one, which is quite helpful for detailed structural analysis of complex lipids. All other important product ions found are described in detail (following our previously published glycerophospholipid product ion nomenclature; Pittenauer and Allmaier, Int. J. Mass. Spectrom. 301:90-1012, 2011).

Optical characterization of poly(methyl methacrylate) implanted with low energy ions

NASA Astrophysics Data System (ADS)

Gupta, Renu; Kumar, Vijay; Goyal, Parveen Kumar; Kumar, Shyam

2012-12-01

The samples of poly(methyl methacrylate) (PMMA) were subjected to 100 keV N+ and Ar+ ion implantation up to a maximum fluence of 2 × 1016 ions/cm2. The effect of ion implantation on the optical energy gap and the refractive index has been studied through UV-visible spectroscopy. The results clearly indicate a decrease in the values of optical energy gap and an increase in the values of refractive index as an effect of ion implantation corresponding to both of the ions. It has also been observed that the changes induced by the implanted ions are more pronounced for N+ ions in comparison to Ar+ ions. This variation has been correlated with the calculated ranges of these ions in PMMA polymer using Stopping and Range of Ions in Matter (SRIM) code. Finally, an attempt has been made to correlate all the observed changes with the induced structural changes as revealed through Raman spectroscopy.

Characterizing multiple metal ion binding sites within a ribozyme by cadmium-induced EPR silencing

PubMed Central

Kisseleva, Natalia; Kraut, Stefanie; Jäschke, Andres; Schiemann, Olav

2007-01-01

In ribozyme catalysis, metal ions are generally known to make structural and∕or mechanistic contributions. The catalytic activity of a previously described Diels-Alderase ribozyme was found to depend on the concentration of divalent metal ions, and crystallographic data revealed multiple binding sites. Here, we elucidate the interactions of this ribozyme with divalent metal ions in solution using electron paramagnetic resonance (EPR) spectroscopy. Manganese ion titrations revealed five high-affinity Mn2+ binding sites with an upper Kd of 0.6±0.2 μM. In order to characterize each binding site individually, EPR-silent Cd2+ ions were used to saturate the other binding sites. This cadmium-induced EPR silencing showed that the Mn2+ binding sites possess different affinities. In addition, these binding sites could be assigned to three different types, including innersphere, outersphere, and a Mn2+ dimer. Based on simulations, the Mn2+-Mn2+ distance within the dimer was found to be ∼6 Å, which is in good agreement with crystallographic data. The EPR-spectroscopic characterization reveals no structural changes upon addition of a Diels-Alder product, supporting the concept of a preorganized catalytic pocket in the Diels-Alder ribozyme and the structural role of these ions. PMID:19404418

Characterization of epoxy carotenoids by fast atom bombardment collision-induced dissociation MS/MS.

PubMed

Maoka, Takashi; Fujiwara, Yasuhiro; Hashimoto, Keiji; Akimoto, Naoshige

2004-02-01

The characterization and structure of epoxy carotenoids possessing 5,6-epoxy, 5,8-epoxy and 3,6-epoxy end groups conjugated to the polyene chain were investigated using high-energy fast atom bombardment collision-induced dissociation MS/MS methods. In addition to [M - 80](+*), a characteristic fragment ion of an epoxy carotenoid, product ions resulting from the cleavage of C-C bonds in the polyene chain from the epoxy end group, such as m/z 181 (b ion) and 121 (c ion), were detected. On the other hand, diagnostic ions of m/z 286 (e-H ion) and 312 (f-H ion) were observed, not in the 5,6-epoxy or 5,8-epoxy carotenoid but in the 3,6-epoxy carotenoid. These fragmentation patterns can be used to distinguish 3,6-epoxy carotenoids from 5,6-epoxy or 5,8-epoxy carotenoids. The structure of an epoxy carotenoid, 3,6-epoxy-5,6-dihydro-7',8'-didehydro-beta,beta-carotene-5,3'-diol (8), isolated from oyster, was characterized using FAB CID-MS/MS by comparing fragmentation patterns with those of related known compounds.

Irradiation induced structural change in Mo 2Zr intermetallic phase

DOE PAGES

Gan, J.; Keiser, Jr., D. D.; Miller, B. D.; ...

2016-05-14

The Mo 2Zr phase has been identified as a major interaction product at the interface of U-10Mo and Zr. Transmission electron microscopy in-situ irradiation with Kr ions at 200 °C with doses up to 2.0E+16 ions/cm 2 was carried out to investigate the radiation stability of the Mo 2Zr. The Mo 2Zr undergoes a radiation-induced structural change, from a large cubic (cF24) to a small cubic (cI2), along with an estimated 11.2% volume contraction without changing its composition. The structural change begins at irradiation dose below 1.0E+14 ions/cm 2. Furthermore, the transformed Mo 2Zr phase demonstrates exceptional radiation tolerance withmore » the development of dislocations without bubble formation.« less

Modification of the crystal structure of gadolinium gallium garnet by helium ion irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ostafiychuk, B. K.; Yaremiy, I. P., E-mail: yaremiy@rambler.ru; Yaremiy, S. I.

2013-12-15

The structure of gadolinium gallium garnet (GGG) single crystals before and after implantation by He{sup +} ions has been investigated using high-resolution X-ray diffraction methods and the generalized dynamic theory of X-ray scattering. The main types of growth defects in GGG single crystals and radiation-induced defects in the ion-implanted layer have been determined. It is established that the concentration of dislocation loops in the GGG surface layer modified by ion implantation increases and their radius decreases with an increase in the implantation dose.

Fabrication of monolithic microfluidic channels in diamond with ion beam lithography

NASA Astrophysics Data System (ADS)

Picollo, F.; Battiato, A.; Boarino, L.; Ditalia Tchernij, S.; Enrico, E.; Forneris, J.; Gilardino, A.; Jakšić, M.; Sardi, F.; Skukan, N.; Tengattini, A.; Olivero, P.; Re, A.; Vittone, E.

2017-08-01

In the present work, we report on the monolithic fabrication by means of ion beam lithography of hollow micro-channels within a diamond substrate, to be employed for microfluidic applications. The fabrication strategy takes advantage of ion beam induced damage to convert diamond into graphite, which is characterized by a higher reactivity to oxidative etching with respect to the chemically inert pristine structure. This phase transition occurs in sub-superficial layers thanks to the peculiar damage profile of MeV ions, which mostly damage the target material at their end of range. The structures were obtained by irradiating commercial CVD diamond samples with a micrometric collimated C+ ion beam at three different energies (4 MeV, 3.5 MeV and 3 MeV) at a total fluence of 2 × 1016 cm-2. The chosen multiple-energy implantation strategy allows to obtain a thick box-like highly damaged region ranging from 1.6 μm to 2.1 μm below the sample surface. High-temperature annealing was performed to both promote the graphitization of the ion-induced amorphous layer and to recover the pristine crystalline structure in the cap layer. Finally, the graphite was removed by ozone etching, obtaining monolithic microfluidic structures. These prototypal microfluidic devices were tested injecting aqueous solutions and the evidence of the passage of fluids through the channels was confirmed by confocal fluorescent microscopy.

Characterization of ion-induced radiation effects in nuclear materials using synchrotron x-ray techniques

DOE PAGES

Lang, Maik; Tracy, Cameron L.; Palomares, Raul I.; ...

2015-05-01

Recent efforts to characterize the nanoscale structural and chemical modifications induced by energetic ion irradiation in nuclear materials have greatly benefited from the application of synchrotron-based x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) techniques. Key to the study of actinide-bearing materials has been the use of small sample volumes, which are particularly advantageous, as the small quantities minimize the level of radiation exposure at the ion-beam and synchrotron user facility. This approach utilizes energetic heavy ions (energy range: 100 MeV–3 GeV) that pass completely through the sample thickness and deposit an almost constant energy per unit length along theirmore » trajectory. High energy x-rays (25–65 keV) from intense synchrotron light sources are then used in transmission geometry to analyze ion-induced structural and chemical modifications throughout the ion tracks. We describe in detail the experimental approach for utilizing synchrotron radiation (SR) to study the radiation response of a range of nuclear materials (e.g., ThO 2 and Gd 2Ti xZr 2–xO 7). Also addressed is the use of high-pressure techniques, such as the heatable diamond anvil cell, as a new means to expose irradiated materials to well-controlled high-temperature (up to 1000 °C) and/or high-pressure (up to 50 GPa) conditions. Furthermore, this is particularly useful for characterizing the annealing kinetics of irradiation-induced material modifications.« less

Modifications of structural and physical properties induced by swift heavy ions in Gd2Ti2O7 and Y2Ti2O7 pyrochlores

NASA Astrophysics Data System (ADS)

Sellami, N.; Sattonnay, G.; Grygiel, C.; Monnet, I.; Debelle, A.; Legros, C.; Menut, D.; Miro, S.; Simon, P.; Bechade, J. L.; Thomé, L.

2015-12-01

The structural transformations induced by ionization processes in Gd2Ti2O7 and Y2Ti2O7 pyrochlores irradiated with swift heavy ions have been studied using XRD and Raman experiments. Results show that irradiation induces amorphization and that the phase transformation build-up can be accounted for in the framework of a model involving a single-impact mechanism. The radiation induced amorphization build-up is faster in Gd2Ti2O7 than in Y2Ti2O7. Moreover, a decrease of the thermal conductivity (measured by the laser flash method) is induced by irradiation both in Gd2Ti2O7 and Y2Ti2O7.

Electronic excitation induced modifications in elongated iron nanoparticle encapsulated multiwalled carbon nanotubes under ion irradiation

NASA Astrophysics Data System (ADS)

Saikiran, V.; Bazylewski, P.; Sameera, I.; Bhatia, Ravi; Pathak, A. P.; Prasad, V.; Chang, G. S.

2018-05-01

Multi-wall carbon nanotubes (MWCNT) filled with Fe nanorods were shown to have contracted and deformed under heavy ion irradiation. In this study, 120 MeV Ag and 80 MeV Ni ion irradiation was performed to study the deformation and defects induced in iron filled MWCNT under heavy ion irradiation. The structural modifications induced due to electronic excitation by ion irradiation were investigated employing high-resolution transmission electron microscopy, micro-Raman scattering experiments, and synchrotron-based X-ray absorption and emission spectroscopy. We understand that the ion irradiation causes modifications in the Fe nanorods which result in compressions and expansions of the nanotubes, and in turn leads to the buckling of MWCNT. The G band of the Raman spectra shifts slightly towards higher wavenumber and the shoulder G‧ band enhances with the increase of ion irradiation fluence, where the buckling wavelength depends on the radius 'r' of the nanotubes as exp[(r)0.5]. The intensity ratio of the D to G Raman modes initially decreases at the lowest fluence, and then it increases with the increase in ion fluence. The electron diffraction pattern and the high resolution images clearly show the presence of ion induced defects on the walls of the tube and encapsulated iron nanorods.

Investigation of the Structural Stability of Ion-Implanted Gd 2Ti 2-xSn xO 7 Pyrochlore-Type Oxides by Glancing Angle X-ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aluri, Esther Rani; Hayes, John R.; Walker, James D.S.

2016-03-24

Rare-earth titanate and stannate pyrochlore-type oxides have been investigated in the past for the sequestration of nuclear waste elements because of their resistance to radiation-induced structural damage. In order to enhance this property, it is necessary to understand the effect of radioactive decay of the incorporated actinide elements on the local chemical environment. In this study, Gd 2Ti 2–xSn xO 7 materials have been implanted with Au– ions to simulate radiation-induced structural damage. Glancing angle X-ray absorption near-edge spectroscopy (GA-XANES), glancing angle X-ray absorption fine structure (GA-EXAFS) analysis, and powder X-ray diffraction have been used to investigate changes in themore » local coordination environment of the metal atoms in the damaged surface layer. Examination of GA-XANES/EXAFS spectra from the implanted Gd 2Ti 2–xSn xO 7 materials collected at various glancing angles allowed for an investigation of how the local coordination environment around the absorbing atoms changed at different depths in the damaged surface layer. This study has shown the usefulness of GA-XANES to the examination of ion-implanted materials and has suggested that Gd 2Ti 2–xSn xO 7 becomes more susceptible to ion-beam-induced structural damage with increasing Sn concentration.« less

Growth of surface structures correlated with structural and mechanical modifications of brass by laser-induced Si plasma ions implantation

NASA Astrophysics Data System (ADS)

Ahmad, Shahbaz; Bashir, Shazia; Rafique, M. Shahid; Yousaf, Daniel

2017-04-01

Laser-produced Si plasma is employed as an ion source for implantation on the brass substrate for its surface, structural, and mechanical modifications. Thomson parabola technique is employed for the measurement of energy and flux of Si ions using CR-39. In response to stepwise increase in number of laser pulses from 3000 to 12000, four brass substrates were implanted by laser-induced Si plasma ions of energy 290 keV at different fluxes ranging from 45 × 1012 to 75 × 1015 ions/cm2. SEM analysis reveals the formation of nano/micro-sized irregular shaped cavities and pores for the various ion fluxes for varying numbers of laser pulses from 3000 to 9000. At the maximum ion flux for 12,000 pulses, distinct and organized grains with hexagonal and irregular shaped morphology are revealed. X-ray diffractometer (XRD) analysis exhibits that a new phase of CuSi (311) is identified which confirms the implantation of Si ions in brass substrate. A significant decrease in mechanical properties of implanted brass, such as Yield Stress (YS), Ultimate Tensile Strength (UTS), and hardness, with increasing laser pulses from 3000 to 6000 is observed. However, with increasing laser pulses from 9000 to a maximum value of 12,000, an increase in mechanical properties like hardness, YS, and UTS is observed. The generation as well as annihilation of defects, recrystallization, and intermixing of Si precipitates with brass matrix is considered to be responsible for variations in surface, structural, and mechanical modifications of brass.

Fast ion conductivity in strained defect-fluorite structure created by ion tracks in Gd 2Ti 2O 7

DOE PAGES

Aidhy, Dilpuneet S.; Sachan, Ritesh; Zarkadoula, Eva; ...

2015-11-10

In this research, the structure and ion-conducting properties of the defect-fluorite ring structure formed around amorphous ion-tracks by swift heavy ion irradiation of Gd 2Ti 2O 7 pyrochlore are investigated. High angle annular dark field imaging complemented with ion-track molecular dynamics simulations show that the atoms in the ring structure are disordered, and have relatively larger cation-cation interspacing than in the bulk pyrochlore, illustrating the presence of tensile strain in the ring region. Density functional theory calculations show that the non-equilibrium defect-fluorite structure can be stabilized by tensile strain. The pyrochlore to defect-fluorite structure transformation in the ring region ismore » predicted to be induced by recrystallization during a melt-quench process and stabilized by tensile strain. Static pair-potential calculations show that planar tensile strain lowers oxygen vacancy migration barriers in pyrochlores, in agreement with recent studies on fluorite and perovskite materials. From these results, it is suggested that strain engineering could be simultaneously used to stabilize the defect-fluorite structure and gain control over its high ion-conducting properties.« less

Sampling and testing for chloride ion in concrete

DOT National Transportation Integrated Search

1977-08-01

One of the most severe problems facing the highway community is chloride ion-induced reinforcing steel corrosion and the subsequent deterioration of concrete bridge decks and marine structures. This report presents recommended methods for sampling an...

Effects of 200 keV Ar-ions irradiation on the structural and optical properties of reactively sputtered CrN films

NASA Astrophysics Data System (ADS)

Novaković, M.; Popović, M.; Zhang, K.; Rakočević, Z.; Bibić, N.

2016-12-01

Modification in structural and optical properties of chromium-nitride (CrN) films induced by argon ion irradiation and thermal annealings were investigated using various experimental techniques. CrN films deposited by d. c. reactive sputtering on Si substrate were implanted with 200 keV argon ions, at fluences of 5-20 × 1015 ions/cm2. As-implanted samples were then annealed in vacuum, for 2 h at 700 °C. Rutherford backscattering spectrometry, X-ray diffraction, cross-sectional (high-resolution) transmission electron microscopy and spectroscopic ellipsometry (SE) measurements were carried out in order to study structural and optical properties of the layers. After irradiation with 200 keV Ar ions a damaged surface layer of nanocrystalline structure was generated, which extended beyond the implantation profile, but left an undamaged bottom zone. Partial loss of columnar structure observed in implanted samples was recovered after annealing at 700 °C and CrN started to decompose to Cr2N. This layer geometry determined from transmission electron microscopy was inferred in the analysis of SE data using the combined Drude and Tauc-Lorentz model, and the variation of the optical bandgap was deduced. The results are discussed on the basis of the changes induced in the microstructure. It was found that the optical properties of the layers are strongly dependent on the defects' concentration of CrN.

Argon-ion-induced formation of nanoporous GaSb layer: Microstructure, infrared luminescence, and vibrational properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Datta, D. P.; Som, T., E-mail: tsom@iopb.res.in; Kanjilal, A.

2014-07-21

Room temperature implantation of 60 keV Ar{sup +}-ions in GaSb to the fluences of 7 × 10{sup 16} to 3 × 10{sup 18} ions cm{sup −2} is carried out at two incidence angles, viz 0° and 60°, leading to formation of a nanoporous layer. As the ion fluence increases, patches grow on the porous layer under normal ion implantation, whereas the porous layer gradually becomes embedded under a rough top surface for oblique incidence of ions. Grazing incidence x-ray diffraction and cross-sectional transmission electron microscopy studies reveal the existence of nanocrystallites embedded in the ion-beam amorphized GaSb matrix up to the highest fluence used inmore » our experiment. Oxidation of the nanoporous layers becomes obvious from x-ray photoelectron spectroscopy and Raman mapping. The correlation of ion-beam induced structural modification with photoluminescence signals in the infrared region has further been studied, showing defect induced emission of additional peaks near the band edge of GaSb.« less

Strategies to curb structural changes of lithium/transition metal oxide cathode materials & the changes' effects on thermal & cycling stability

DOE PAGES

Yu, Xiqian; Hu, Enyuan; Bak, Seongmin; ...

2015-12-07

Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. Furthermore, we also discuss applying the information about heat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue. As a result, it is widely accepted that the thermal instability of themore » cathodes is one of the most critical factors in thermal runaway and related safety problems.« less

Ion Mobility Measurements of Multianionic Metalloporphyrin Dimers: Structural Changes Induced by Countercation Exchange

NASA Astrophysics Data System (ADS)

Schneider, Erik; Brendle, Katrina; Jäger, Patrick; Weis, Patrick; Kappes, Manfred M.

2018-04-01

We present gas-phase structures of dimers of MnIII and FeIII meso-tetra(4-sulfonatophenyl)porphyrin multianions with various amounts of sodium and hydrogen counterions. The structural assignments are achieved by combining mass spectrometry, ion mobility measurements, quantum chemical calculations, and trajectory method collision cross section calculations. For a common charge state, we observe significant topological variations in the dimer structures of [(MTPPS)2+nX](6-n)- (M=MnIII, FeIII; X=H, Na; n = 1-3) induced by replacing hydrogen counterions by sodium. For sodium, the dimer structures are much more compact, a finding that can be rationalized by the stronger interactions of the sodium cations with the anionic sulfonic acid groups of the porphyrins as compared to hydrogen. [Figure not available: see fulltext.

Variation in the electrical properties of ion beam irradiated cadmium selenate nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chauhan, R. P., E-mail: chauhanrpc@gmail.com; Narula, Chetna; Panchal, Suresh

The key feature of nanowires consists in the pronounced change in properties induced by the low dimensionality and high surface to volume ratio. The study of electrical transport properties of nanowires is important for electronic device applications. Energetic ions create changes, which may be structural or chemical, in a material along their track and these changes might alter the material’s properties. The demand of the modern technology is to understand the effect of radiation on the different properties of the material for its further applications. The present study is on the high-energy Nickel ion beam (160 MeV Ni{sup +12}) induced modificationsmore » in the electrical and structural properties of the cadmium selenate nanowires. An enhancement in the electrical conductivity of irradiated wires was observed as the ion fluence was increased especially in the forward I–V characteristics. The creation of defects by ion irradiation and the synergy of the ions during their passage in the sample with the intrinsic charge carriers may be responsible for the variation in the transport properties of the irradiated nanowires.« less

Ripple structure of crystalline layers in ion-beam-induced Si wafers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hazra, S.; Chini, T.K.; Sanyal, M.K.

Ion-beam-induced ripple formation in Si wafers was studied by two complementary surface sensitive techniques, namely atomic force microscopy (AFM) and depth-resolved x-ray grazing incidence diffraction (GID). The formation of ripple structure at high doses ({approx}7x10{sup 17} ions/cm{sup 2}), starting from initiation at low doses ({approx}1x10{sup 17} ions/cm{sup 2}) of ion beam, is evident from AFM, while that in the buried crystalline region below a partially crystalline top layer is evident from GID study. Such ripple structure of crystalline layers in a large area formed in the subsurface region of Si wafers is probed through a nondestructive technique. The GID techniquemore » reveals that these periodically modulated wavelike buried crystalline features become highly regular and strongly correlated as one increases the Ar ion-beam energy from 60 to 100 keV. The vertical density profile obtained from the analysis of a Vineyard profile shows that the density in the upper top part of ripples is decreased to about 15% of the crystalline density. The partially crystalline top layer at low dose transforms to a completely amorphous layer for high doses, and the top morphology was found to be conformal with the underlying crystalline ripple.« less

Fragmentation studies of fulvic acids using collision induced dissociation fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Witt, Matthias; Fuchser, Jens; Koch, Boris P

2009-04-01

The complex natural organic matter standard Suwannee river fulvic acid (SRFA) was analyzed by negative ion mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS) using on-resonance collision induced dissociation (CID) of single ultrahigh resolved mass peaks in the ICR cell. Molecular formula assignment of precursor masses resulted in exactly one molecular formula for each of the peaks. Analyses of the corresponding fragment spectra and comparison to different standard substances revealed specific neutral losses and fragmentation patterns which result in structures consisting of a high degree of carboxyl- and fewer hydroxyl groups. The comparison of fragmented mass peaks within different pseudohomologous series (CH(2)-series, and CH(4) vs O exchange) suggested structurally based differences between these series. CID FTICR MS allowed isolating single mass peaks in a very complex natural organic matter spectrum. Subsequently, fragmentation gave structural insights into this material. Our results suggest that the structural diversity in complex humic substances is not as high as expected.

Effects of low and high energy ion bombardment on ETFE polymer

NASA Astrophysics Data System (ADS)

Minamisawa, R. A.; De Almeida, A.; Abidzina, V.; Parada, M. A.; Muntele, I.; Ila, D.

2007-04-01

The polymer ethylenetetrafluoroethylene (ETFE) is used as anti-adherent coatings for food packages and radiation dosimeters. In this work, we compare the damage induced in ETFE bombarded with 100 keV Si ions with that induced by 1 MeV proton bombardment. The damage depends on the type, energy and intensity of the irradiation. Irradiated films were analyzed with optical absorption photospectrometry, Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy to determine the chemical nature of the structural changes caused by ion irradiation. Computer simulations were performed to evaluate the radiation damage.

Separation and identification of structural isomers by quadrupole collision-induced dissociation-hydrogen/deuterium exchange-infrared multiphoton dissociation (QCID-HDX-IRMPD).

PubMed

Gucinski, Ashley C; Somogyi, Arpád; Chamot-Rooke, Julia; Wysocki, Vicki H

2010-08-01

A new approach that uses a hybrid Q-FTICR instrument and combines quadrupole collision-induced dissociation, hydrogen-deuterium exchange, and infrared multiphoton dissociation (QCID-HDX-IRMPD) has been shown to effectively separate and differentiate isomeric fragment ion structures present at the same m/z. This method was used to study protonated YAGFL-OH (free acid), YAGFL-NH(2) (amide), cyclic YAGFL, and YAGFL-OCH(3) (methyl ester). QCID-HDX of m/z 552.28 (C(29)H(38)N(5)O(6)) from YAGFL-OH reveals at least two distributions of ions corresponding to the b(5) ion and a non-C-terminal water loss ion structure. Subsequent IRMPD fragmentation of each population shows distinct fragmentation patterns, reflecting the different structures from which they arise. This contrasts with data for YAGFL-NH(2) and YAGFL-OCH(3), which do not show two distinct H/D exchange populations for the C(29)H(38)N(5)O(6) structure formed by NH(3) and HOCH(3) loss, respectively. Relative extents of exchange for C(29)H(38)N(5)O(6) ions from six sequence isomers (YAGFL, AGFLY, GFLYA, FLYAG, LYAGF, and LFGAY) show a sequence dependence of relative isomer abundance. Supporting action IRMPD spectroscopy data are also presented herein and also show that multiple structures are present for the C(29)H(38)N(5)O(6) species from YAGFL-OH. Copyright 2010. Published by Elsevier Inc.

Forging Fast Ion Conducting Nanochannels with Swift Heavy Ions: The Correlated Role of Local Electronic and Atomic Structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sachan, Ritesh; Cooper, Valentino R.; Liu, Bin

2016-12-19

Atomically disordered oxides have attracted significant attention in recent years due to the possibility of enhanced ionic conductivity. However, the correlation between atomic disorder, corresponding electronic structure, and the resulting oxygen diffusivity is not well understood. The disordered variants of the ordered pyrochlore structure in gadolinium titanate (Gd 2Ti 2O 7) are seen as a particularly interesting prospect due to intrinsic presence of a vacant oxygen site in the unit atomic structure, which could provide a channel for fast oxygen conduction. In this paper, we provide insights into the subangstrom scale on the disordering-induced variations in the local atomic environmentmore » and its effect on the electronic structure in high-energy ion irradiation-induced disordered nanochannels, which can be utilized as pathways for fast oxygen ion transport. With the help of an atomic plane-by-plane-resolved analyses, the work shows how the presence of various types of TiO x polyhedral that exist in the amorphous and disordered crystalline phase modify the electronic structures relative to the ordered pyrochlore phase in Gd 2Ti 2O 7. Finally, the correlated molecular dynamics simulations on the disordered structures show a remarkable enhancement in oxygen diffusivity as compared with ordered pyrochlore lattice and make that a suitable candidate for applications requiring fast oxygen conduction.« less

Ion/Neutral, Ion/Electron, Ion/Photon, and Ion/Ion Interactions in Tandem Mass Spectrometry: Do we need them all? Are they enough?

PubMed Central

McLuckey, Scott A.; Mentinova, Marija

2011-01-01

A range of strategies and tools has been developed to facilitate the determination of primary structures of analyte molecules of interest via tandem mass spectrometry (MS/MS). The two main factors that determine the primary structural information present in an MS/MS spectrum are the type of ion generated from the analyte molecule and the dissociation method. The ion-type subjected to dissociation is determined by the ionization method/conditions and ion transformation processes that might take place after initial gas-phase ion formation. Furthermore, the range of analyte-related ion types can be expanded via derivatization reactions prior to mass spectrometry. Dissociation methods include those that simply alter the population of internal states of the mass-selected ion (i.e., activation methods like collision-induced dissociation) as well as processes that rely on transformation of the ion-type prior to dissociation (e.g., electron capture dissociation). A variety of ionic interactions has been studied for the purpose of ion dissociation and ion transformation that include ion/neutral, ion/photon, ion/electron, and ion/ion interactions. A wide range of phenomena has been observed, many of which have been explored/developed as means for structural analysis. The techniques arising from these phenomena are discussed within the context of the elements of structure determination in tandem mass spectrometry, viz., ion-type definition and dissociation. Unique aspects of the various ion interactions are emphasized along with any barriers to widespread implementation. PMID:21472539

Collision Cross Sections and Ion Mobility Separation of Fragment Ions from Complex N-Glycans.

PubMed

Harvey, David J; Watanabe, Yasunori; Allen, Joel D; Rudd, Pauline; Pagel, Kevin; Crispin, Max; Struwe, Weston B

2018-06-01

Ion mobility mass spectrometry (IM-MS) holds great potential for structural glycobiology, in particular in its ability to resolve glycan isomers. Generally, IM-MS has largely been applied to intact glycoconjugate ions with reports focusing on the separation of different adduct types. Here, we explore IM separation and report the collision cross section (CCS) of complex type N-glycans and their fragments in negative ion mode following collision-induced dissociation (CID). CCSs of isomeric fragment ions were found, in some cases, to reveal structural details that were not present in CID spectra themselves. Many fragment ions were confirmed as possessing multiple structure, details of which could be obtained by comparing their drift time profiles to different glycans. By using fragmentation both before and after mobility separation, information was gathered on the fragmentation pathways producing some of the ions. These results help demonstrate the utility of IM and will contribute to the growing use of IM-MS for glycomics. Graphical Abstract ᅟ.

Collision Cross Sections and Ion Mobility Separation of Fragment Ions from Complex N-Glycans

NASA Astrophysics Data System (ADS)

Harvey, David J.; Watanabe, Yasunori; Allen, Joel D.; Rudd, Pauline; Pagel, Kevin; Crispin, Max; Struwe, Weston B.

2018-04-01

Ion mobility mass spectrometry (IM-MS) holds great potential for structural glycobiology, in particular in its ability to resolve glycan isomers. Generally, IM-MS has largely been applied to intact glycoconjugate ions with reports focusing on the separation of different adduct types. Here, we explore IM separation and report the collision cross section (CCS) of complex type N-glycans and their fragments in negative ion mode following collision-induced dissociation (CID). CCSs of isomeric fragment ions were found, in some cases, to reveal structural details that were not present in CID spectra themselves. Many fragment ions were confirmed as possessing multiple structure, details of which could be obtained by comparing their drift time profiles to different glycans. By using fragmentation both before and after mobility separation, information was gathered on the fragmentation pathways producing some of the ions. These results help demonstrate the utility of IM and will contribute to the growing use of IM-MS for glycomics. [Figure not available: see fulltext.

Oxygen ion implantation induced microstructural changes and electrical conductivity in Bakelite RPC detector material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, K. V. Aneesh, E-mail: aneesh1098@gmail.com; Ravikumar, H. B., E-mail: hbr@physics.uni-mysore.ac.in; Ranganathaiah, C., E-mail: cr@physics.uni-mysore.ac.in

2016-05-06

In order to explore the structural modification induced electrical conductivity, samples of Bakelite Resistive Plate Chamber (RPC) detector materials were exposed to 100 keV Oxygen ion in the fluences of 10{sup 12}, 10{sup 13}, 10{sup 14} and 10{sup 15} ions/cm{sup 2}. Ion implantation induced microstructural changes have been studied using Positron Annihilation Lifetime Spectroscopy (PALS) and X-Ray Diffraction (XRD) techniques. Positron lifetime parameters viz., o-Ps lifetime and its intensity shows the deposition of high energy interior track and chain scission leads to the formation of radicals, secondary ions and electrons at lower ion implantation fluences (10{sup 12} to10{sup 14} ions/cm{supmore » 2}) followed by cross-linking at 10{sup 15} ions/cm{sup 2} fluence due to the radical reactions. The reduction in electrical conductivity of Bakelite detector material is correlated to the conducting pathways and cross-links in the polymer matrix. The appropriate implantation energy and fluence of Oxygen ion on polymer based Bakelite RPC detector material may reduce the leakage current, improves the efficiency, time resolution and thereby rectify the aging crisis of the RPC detectors.« less

Understanding of the mechanical and structural changes induced by alpha particles and heavy ions in the French simulated nuclear waste glass

NASA Astrophysics Data System (ADS)

Karakurt, G.; Abdelouas, A.; Guin, J.-P.; Nivard, M.; Sauvage, T.; Paris, M.; Bardeau, J.-F.

2016-07-01

Borosilicate glasses are considered for the long-term confinement of high-level nuclear wastes. External irradiations with 1 MeV He+ ions and 7 MeV Au5+ ions were performed to simulate effects produced by alpha particles and by recoil nuclei in the simulated SON68 nuclear waste glass. To better understand the structural modifications, irradiations were also carried out on a 6-oxides borosilicate glass, a simplified version of the SON68 glass (ISG glass). The mechanical and macroscopic properties of the glasses were studied as function of the deposited electronic and nuclear energies. Alpha particles and gold ions induced a volume change up to -0.7% and -2.7%, respectively, depending on the glass composition. Nano-indentations tests were used to determine the mechanical properties of the irradiated glasses. A decrease of about -22% to -38% of the hardness and a decrease of the reduced Young's modulus by -8% were measured after irradiations. The evolution of the glass structure was studied by Raman spectroscopy, and also 11B and 27Al Nuclear Magnetic Resonance (MAS-NMR) on a 20 MeV Kr irradiated ISG glass powder. A decrease of the silica network connectivity after irradiation with alpha particles and gold ions is deduced from the structural changes observations. NMR spectra revealed a partial conversion of BO4 to BO3 units but also a formation of AlO5 and AlO6 species after irradiation with Kr ions. The relationships between the mechanical and structural changes are also discussed.

Optical properties of Si+ implanted PMMA

NASA Astrophysics Data System (ADS)

Balabanov, S.; Tsvetkova, T.; Borisova, E.; Avramov, L.; Bischoff, L.; Zuk, J.

2010-04-01

In the present work, low energy ion beam irradiation was used for surface modification of polymethyl-methacrylate (PMMA) using silicon (Si+) as the ion species. After high doses ion implantation of Si+ in the polymer material, a characterization of the optical properties was performed using optical transmission measurements in the visible and near infra-red (IR) wavelength range. The optical absorption increase observed with the ion dose was attributed to ion beam induced structural changes in the modified material.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Jing-Yun, E-mail: jyunwu@ncnu.edu.tw; Tsai, Chi-Jou; Chang, Ching-Yun

A Zn(II)−salicylaldimine complex [Zn(L{sup salpyca})(H{sub 2}O)]{sub n} (1, where H{sub 2}L{sup salpyca}=4-hydroxy-3-(((pyridin-2-yl)methylimino)methyl)benzoic acid), with a one-dimensional (1D) chain structure, has been successfully converted to a discrete Ni(II)−salicylaldimine complex [Ni(L{sup salpyca})(H{sub 2}O){sub 3}] (2) and an infinite Cu(II)−salicylaldimine complex ([Cu(L{sup salpyca})]·3H{sub 2}O){sub n} (3) through a metal-ion exchange induced structural transformation process. However, such processes do not worked by Mn(II) and Co(II) ions. Solid-state structure analyses reveal that complexes 1–3 form comparable coordinative or supramolecular zigzag chains running along the crystallographic [201] direction. In addition, replacing Zn(II) ion by Ni(II) and Cu(II) ions caused changes in coordination environment and sphere ofmore » metal centers, from a 5-coordinate intermediate geometry of square pyramidal and trigonal bipyramidal in 1 to a 6-coordinate octahedral geometry in 2, and to a 4-coordiante square planar geometry in 3. This study shows that metal-ion exchange serves as a very efficient way of forming new coordination complexes that may not be obtained through direct synthesis. - Graphical abstract: A Zn(II)−salicylaldimine zigzag chain has been successfully converted to a Ni(II)−salicylaldimine supramolecular zigzag chain and a Cu(II)−salicylaldimine coordinative zigzag chain through metal-ion exchange induced structural transformations, which is not achieved by Mn(II) and Co(II) ions.« less

Surface topographical and structural analysis of Ag+-implanted polymethylmethacrylate

NASA Astrophysics Data System (ADS)

Arif, Shafaq; Rafique, M. Shahid; Saleemi, Farhat; Naab, Fabian; Toader, Ovidiu; Sagheer, Riffat; Bashir, Shazia; Zia, Rehana; Siraj, Khurram; Iqbal, Saman

2016-08-01

Specimens of polymethylmethacrylate (PMMA) were implanted with 400-keV Ag+ ions at different ion fluences ranging from 1 × 1014 to 5 × 1015 ions/cm2 using a 400-kV NEC ion implanter. The surface topographical features of the implanted PMMA were investigated by a confocal microscope. Modifications in the structural properties of the implanted specimens were analyzed in comparison with pristine PMMA by X-ray diffraction (XRD) and Raman spectroscopy. UV-Visible spectroscopy was applied to determine the effects of ion implantation on optical transmittance of the implanted PMMA. The confocal microscopic images revealed the formation of hillock-like microstructures along the ion track on the implanted PMMA surface. The increase in ion fluence led to more nucleation of hillocks. The XRD pattern confirmed the amorphous nature of pristine and implanted PMMA, while the Raman studies justified the transformation of Ag+-implanted PMMA into amorphous carbon at the ion fluence of ⩾5 × 1014 ions/cm2. Moreover, the decrease in optical transmittance of PMMA is associated with the formation of hillocks and ion-induced structural modifications after implantation.

Radiation Resistance of the U(Al, Si)3 Alloy: Ion-Induced Disordering

PubMed Central

Yaniv, Gili; Horak, Pavel; Vacik, Jiri; Mykytenko, Natalia; Rafailov, Gennady; Dahan, Itzchak; Fuks, David; Kiv, Arik

2018-01-01

During the exploitation of nuclear reactors, various U-Al based ternary intermetallides are formed in the fuel-cladding interaction layer. Structure and physical properties of these intermetallides determine the radiation resistance of cladding and, ultimately, the reliability and lifetime of the nuclear reactor. In current research, U(Al, Si)3 composition was studied as a potential constituent of an interaction layer. Phase content of the alloy of an interest was ordered U(Al, Si)3, structure of which was reported earlier, and pure Al (constituting less than 20 vol % of the alloy). This alloy was investigated prior and after the irradiation performed by Ar ions at 30 keV. The irradiation was performed on the transmission electron microscopy (TEM, JEOL, Japan) samples, characterized before and after the irradiation process. Irradiation induced disorder accompanied by stress relief. Furthermore, it was found that there is a dose threshold for disordering of the crystalline matter in the irradiated region. Irradiation at doses equal or higher than this threshold resulted in almost solely disordered phase. Using the program “Stopping and Range of Ions in Matter” (SRIM), the parameters of penetration of Ar ions into the irradiated samples were estimated. Based on these estimations, the dose threshold for ion-induced disordering of the studied material was assessed. PMID:29393870

Radiation Resistance of the U(Al, Si)₃ Alloy: Ion-Induced Disordering.

PubMed

Meshi, Louisa; Yaniv, Gili; Horak, Pavel; Vacik, Jiri; Mykytenko, Natalia; Rafailov, Gennady; Dahan, Itzchak; Fuks, David; Kiv, Arik

2018-02-02

During the exploitation of nuclear reactors, various U-Al based ternary intermetallides are formed in the fuel-cladding interaction layer. Structure and physical properties of these intermetallides determine the radiation resistance of cladding and, ultimately, the reliability and lifetime of the nuclear reactor. In current research, U(Al, Si)₃ composition was studied as a potential constituent of an interaction layer. Phase content of the alloy of an interest was ordered U(Al, Si)₃, structure of which was reported earlier, and pure Al (constituting less than 20 vol % of the alloy). This alloy was investigated prior and after the irradiation performed by Ar ions at 30 keV. The irradiation was performed on the transmission electron microscopy (TEM, JEOL, Japan) samples, characterized before and after the irradiation process. Irradiation induced disorder accompanied by stress relief. Furthermore, it was found that there is a dose threshold for disordering of the crystalline matter in the irradiated region. Irradiation at doses equal or higher than this threshold resulted in almost solely disordered phase. Using the program "Stopping and Range of Ions in Matter" (SRIM), the parameters of penetration of Ar ions into the irradiated samples were estimated. Based on these estimations, the dose threshold for ion-induced disordering of the studied material was assessed.

Investigations of glass structure using fluorescence line narrowing and moleuclar dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weber, M.J.; Brawer, S.A.

1982-07-02

The local structure at individual ion sites in simple and multicomponent glasses is simulated using methods of molecular dynamics. Computer simulations of fluoroberyllate glasses predict a range of ion separations and coordination numbers that increases with increasing complexity of the glass composition. This occurs at both glass forming and glass modifying cation sites. Laser-induced fluorescence line-narrowing techniques provide a unique probe of the local environments of selected subsets of ions and are used to measure site to site variations in the electronic energy levels and transition probabilities of rare earth ions. These and additional results from EXAFS, neutron and x-raymore » diffraction, and NMR experiments are compared with simulated glass structures.« less

Re-crystallization of ITO films after carbon irradiation

NASA Astrophysics Data System (ADS)

Usman, Muhammad; Khan, Shahid; Khan, Majid; Abbas, Turab Ali

2017-01-01

2.0 MeV carbon ion irradiation effects on Indium Tin Oxide (ITO) thin films on glass substrate are investigated. The films are irradiated with carbon ions in the fluence range of 1 × 1013 to 1 × 1015 ions/cm2. The irradiation induced effects in ITO are compared before and after ion bombardment by systematic study of structural, optical and electrical properties of the films. The XRD results show polycrystalline nature of un-irradiated ITO films which turns to amorphous state after 1 × 1013 ions/cm2 fluence of carbon ions. Further increase in ion fluence to 1 × 1014 ions/cm2 re-crystallizes the structure and retains for even higher fluences. A gradual decrease in the electrical conductivity and transmittance of irradiated samples is observed with increasing ion fluence. The band gap of the films is observed to be decreased after carbon irradiation.

A novel method for study of the aggregation of protein induced by metal ion aluminum(III) using resonance Rayleigh scattering technique

NASA Astrophysics Data System (ADS)

Long, Xiufen; Zhang, Caihua; Cheng, Jiongjia; Bi, Shuping

2008-01-01

We present a novel method for the study of the aggregation of protein induced by metal ion aluminum(III) using resonance Rayleigh scattering (RRS) technique. In neutral Tris-HCl medium, the effect of this aggregation of protein results in the enhancement of RRS intensity and the relationship between the enhancement of the RRS signal and the Al concentration is nonlinear. On this basis, we established a new method for the determination of the critical induced-aggregation concentrations ( CCIAC) of metal ion Al(III) inducing the protein aggregation. Our results show that many factors, such as, pH value, anions, salts, temperature and solvents have obvious effects. We also studied the extent of aggregation and structural changes using ultra-violet spectrometry, protein intrinsic fluorescence and circular dichroism to further understand the exact mechanisms of the aggregation characteristics of proteins induced by metal ion Al(III) at the molecular level, to help us to develop effective methods to investigate the toxicity of metal ion Al, and to provide theoretical and quantitative evidences for the development of appropriate treatments for neurodementia such as Parkinson's disease, Alzheimer's disease and dementia related to dialysis.

Study on swift heavy ions induced modifications of Ag-ZnO nanocomposite thin film

NASA Astrophysics Data System (ADS)

Singh, S. K.; Singhal, R.; Siva Kumar, V. V.

2017-03-01

In the present work, swift heavy ion (SHI) irradiation induced modifications in structural and optical properties of Ag-ZnO nanocomposite thin films have been investigated. Ag-ZnO nanocomposite (NCs) thin films were synthesized by RF magnetron sputtering technique and irradiated with 100 MeV Ag7+ ions at three different fluences 3 × 1012, 1 × 1013 and 3 × 1013 ions/cm2. Rutherford Backscattering Spectrometry revealed Ag concentration to be ∼8.0 at.%, and measured thickness of the films was ∼55 nm. Structural properties of pristine and irradiated films have been analyzed by X-ray diffraction analysis and found that variation in crystallite size of the film with ion irradiation. X-ray photoelectron spectroscopy (XPS) indicates the formation of Ag-ZnO nanocomposite thin film with presence of Ag, Zn and O elements. Oxidation state of Ag and Zn also estimated by XPS analysis. Surface plasmon resonance (SPR) of Ag nanoparticle has appeared at ∼475 nm in the pristine thin film, which is blue shifted by ∼30 nm in film irradiated at fluence of 3 × 1012 ions/cm2 and completely disappeared in film irradiated at higher fluences, 1 × 1013 and 3 × 1013 ions/cm2. A marginal change in the optical band gap of Ag-ZnO nanocomposite thin film is also found with increasing ion fluence. Surface morphology of pristine and irradiated films have been studied using Atomic Force Microscopy (AFM). Raman and Photo-luminance (PL) spectra of nanocomposite thin films have been investigated to understand the ion induced modifications such as lattice defects and disordering in the nanocomposite thin film.

Track Structure and the Biological Effectiveness of Accelerated Particles for the Induction of Chromosome Damage

NASA Technical Reports Server (NTRS)

George, K.; Hada, M.; Chappell, L.; Cucinotta, F. A.

2011-01-01

Track structure models predict that at a fixed value of LET, particles with lower charge number, Z will have a higher biological effectiveness compared to particles with a higher Z. In this report we investigated how track structure effects induction of chromosomal aberration in human cells. Human lymphocytes were irradiated in vitro with various energies of accelerated iron, silicon, neon, or titanium ions and chromosome damage was assessed in using three color FISH chromosome painting in chemically induced PCC samples collected a first cell division post irradiation. The LET values for these ions ranged from 30 to195 keV/micron. Of the particles studied, Neon ions have the highest biological effectiveness for induction of total chromosome damage, which is consistent with track structure model predictions. For complex-type exchanges 64 MeV/ u Neon and 450 MeV/u Iron were equally effective and induced the most complex damage. In addition we present data on chromosomes exchanges induced by six different energies of protons (5 MeV/u to 2.5 GeV/u). The linear dose response term was similar for all energies of protons suggesting that the effect of the higher LET at low proton energies is balanced by the production of nuclear secondaries from the high energy protons.

Surface and structure modification induced by high energy and highly charged uranium ion irradiation in monocrystal spinel

NASA Astrophysics Data System (ADS)

Yang, Yitao; Zhang, Chonghong; Song, Yin; Gou, Jie; Zhang, Liqing; Meng, Yancheng; Zhang, Hengqing; Ma, Yizhun

2014-05-01

Due to its high temperature properties and relatively good behavior under irradiation, magnesium aluminate spinel (MgAl2O4) is considered as a possible material to be used as inert matrix for the minor actinides burning. In this case, irradiation damage is an unavoidable problem. In this study, high energy and highly charged uranium ions (290 MeV U32+) were used to irradiate monocrystal spinel to the fluence of 1.0 × 1013 ions/cm2 to study the modification of surface and structure. Highly charged ions carry large potential energy, when they interact with a surface, the release of potential energy results in the modification of surface. Atomic force microscopy (AFM) results showed the occurrence of etching on surface after uranium ion irradiation. The etching depth reached 540 nm. The surprising efficiency of etching is considered to be induced by the deposition of potential energy with high density. The X-ray diffraction results showed that the (4 4 0) diffraction peak obviously broadened after irradiation, which indicated that the distortion of lattice has occurred. After multi-peak Gaussian fitting, four Gaussian peaks were separated, which implied that a structure with different damage layers could be formed after irradiation.

Ion beam modification of topological insulator bismuth selenide

DOE PAGES

Sharma, Peter Anand; Sharma, A. L. Lima; Hekmaty, Michelle A.; ...

2014-12-17

In this study, we demonstrate chemical doping of a topological insulator Bi 2Se 3 using ion implantation. Ion beam-induced structural damage was characterized using grazing incidence X-ray diffraction and transmission electron microscopy. Ion damage was reversed using a simple thermal annealing step. Carrier-type conversion was achieved using ion implantation followed by an activation anneal in Bi 2Se 3 thin films. These two sets of experiments establish the feasibility of ion implantation for chemical modification of Bi 2Se 3, a prototypical topological insulator. Ion implantation can, in principle, be used for any topological insulator. The direct implantation of dopants should allowmore » better control over carrier concentrations for the purposes of achieving low bulk conductivity. Ion implantation also enables the fabrication of inhomogeneously doped structures, which in turn should make possible new types of device designs.« less

Collision induced unfolding of isolated proteins in the gas phase: past, present, and future.

PubMed

Dixit, Sugyan M; Polasky, Daniel A; Ruotolo, Brandon T

2018-02-01

Rapidly characterizing the three-dimensional structures of proteins and the multimeric machines they form remains one of the great challenges facing modern biological and medical sciences. Ion mobility-mass spectrometry based techniques are playing an expanding role in characterizing these functional complexes, especially in drug discovery and development workflows. Despite this expansion, ion mobility-mass spectrometry faces many challenges, especially in the context of detecting small differences in protein tertiary structure that bear functional consequences. Collision induced unfolding is an ion mobility-mass spectrometry method that enables the rapid differentiation of subtly-different protein isoforms based on their unfolding patterns and stabilities. In this review, we summarize the modern implementation of such gas-phase unfolding experiments and provide an overview of recent developments in both methods and applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Plasmonic activity on gold nanoparticles embedded in nanopores formed in a surface layer of silica glass by swift-heavy-ion irradiation.

PubMed

Nomura, Ken-ichi; Ohki, Yoshimichi; Fujimaki, Makoto; Wang, Xiaomin; Awazu, Koichi; Komatsubara, Tetsuro

2009-11-25

Silica glass was irradiated by swift heavy ions by selecting the ion species and its energy in order to induce the largest damaged regions. These regions were then selectively etched by hydrofluoric acid vapour to form nanopores on the glass surface. Subsequently, gold nanoparticles were embedded into the nanopores by vacuum evaporation, followed by thermal treatment. In the new plasmonic structure obtained with these procedures, the localized surface plasmon excitation wavelength induced around the gold nanoparticles was found to show a redshift, which agreed well with the theoretical calculation, when water was introduced into the nanopores. This indicates that the fabricated structure can be used as a sensing element to detect the adhesion of substances such as biomolecules to the nanoparticles by measuring the redshift.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage.

PubMed

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; Neuefeind, Joerg; Xu, Wenqian; Teng, Xiaowei

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate of 5 mV s -1 , corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full cells after 5,000 cycles at 10 C). The promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE PAGES

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; ...

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Gamma and Ion-Beam Irradiation of DNA: Free Radical Mechanisms, Electron Effects, and Radiation Chemical Track Structure

PubMed Central

Sevilla, Michael D.; Becker, David; Kumar, Anil; Adhikary, Amitava

2016-01-01

The focus of our laboratory’s investigation is to study the direct-type DNA damage mechanisms resulting from γ-ray and ion-beam radiation-induced free radical processes in DNA which lead to molecular damage important to cellular survival. This work compares the results of low LET (γ−) and high LET (ion-beam) radiation to develop a chemical track structure model for ion-beam radiation damage to DNA. Recent studies on protonation states of cytosine cation radicals in the N1-substituted cytosine derivatives in their ground state and 5-methylcytosine cation radicals in ground as well as in excited state are described. Our results exhibit a radical signature of excitations in 5-methylcytosine cation radical. Moreover, our recent theoretical studies elucidate the role of electron-induced reactions (low energy electrons (LEE), presolvated electrons (epre−), and aqueous (or, solvated) electrons (eaq−)). Finally DFT calculations of the ionization potentials of various sugar radicals show the relative reactivity of these species. PMID:27695205

Gamma and ion-beam irradiation of DNA: Free radical mechanisms, electron effects, and radiation chemical track structure

NASA Astrophysics Data System (ADS)

Sevilla, Michael D.; Becker, David; Kumar, Anil; Adhikary, Amitava

2016-11-01

The focus of our laboratory's investigation is to study the direct-type DNA damage mechanisms resulting from γ-ray and ion-beam radiation-induced free radical processes in DNA which lead to molecular damage important to cellular survival. This work compares the results of low LET (γ-) and high LET (ion-beam) radiation to develop a chemical track structure model for ion-beam radiation damage to DNA. Recent studies on protonation states of cytosine cation radicals in the N1-substituted cytosine derivatives in their ground state and 5-methylcytosine cation radicals in ground as well as in excited state are described. Our results exhibit a radical signature of excitations in 5-methylcytosine cation radical. Moreover, our recent theoretical studies elucidate the role of electron-induced reactions (low energy electrons (LEE), presolvated electrons (epre-), and aqueous (or, solvated) electrons (eaq-)). Finally DFT calculations of the ionization potentials of various sugar radicals show the relative reactivity of these species.

Matrix-Assisted Laser Desorption/Ionisation - High-Energy Collision-Induced Dissociation of Steroids: Analysis of Oxysterols in Rat Brain

PubMed Central

Wang, Yuqin; Hornshaw, Martin; Alvelius, Gunvor; Bodin, Karl; Liu, Suya; Sjövall, Jan; Griffiths, William J.

2008-01-01

Neutral steroids have traditionally been analysed by gas chromatography – mass spectrometry (GC-MS) after necessary derivatisation reactions. However, GC-MS is unsuitable for the analysis of many conjugated steroids and those with unsuspected functional groups. Here we describe an alternative analytical method specifically designed for the analysis of oxosteroids and those with a 3β-hydroxy-Δ5 or 5α-hydrogen-3β-hydroxy structure. Steroids were derivatised with Girard P (GP) hydrazine to give GP hydrazones which are charged species and readily analysed by matrix-assisted laser desorption/ionization mass spectrometry. The resulting [M]+ ions were then subjected to high-energy collision-induced dissociation on a tandem time-of-flight instrument. The product-ion spectra give structurally informative fragment-ion patterns. The sensitivity of the analytical method is such that steroids structures can be determined from low pg (low fmole) amounts of sample. The utility of the method has been demonstrated by the analysis of oxysterols extracted from rat brain. PMID:16383324

On the 16O 6+ ion irradiation induced magnetic moment generation in ZnFe2O4 nano ferrite

NASA Astrophysics Data System (ADS)

Satalkar, M.; Kane, S. N.; Raghuvanshi, S.

2018-05-01

X-ray diffraction (XRD) was utilized to study the effect of 80 MeV 16O 6+ ion irradiation of the as-burnt ZnFe2O4 samples, prepared by sol-gel auto-combustion technique. The samples were irradiated at fluence: 1 × 1011, 1 × 1012, 1 × 1013, 1 × 1014 ions/cm2 to observe the effect of irradiation on structural properties and cationic distribution. XRD confirms the formation of single phase nanocrystalline cubic spinel ferrites with Scherrer's particle diameter (D) ranging between 15.7 - 17.4 nm. Results very distinctly show the electronic energy loss induced changes in: - experimental and theoretical lattice parameter (aexp., ath.), tetrahedral and octahedral bond length (RA, RB), and shared tetrahedral and octahedral edge (dAE, dBE). The paper reports the generation of magnetic moment of Zn ferrite by swift heavy ion irradiation induced distortion at tetrahedral site.

Swift heavy ion-induced radiation damage in isotropic graphite studied by micro-indentation and in-situ electrical resistivity

NASA Astrophysics Data System (ADS)

Hubert, Christian; Voss, Kay Obbe; Bender, Markus; Kupka, Katharina; Romanenko, Anton; Severin, Daniel; Trautmann, Christina; Tomut, Marilena

2015-12-01

Due to its excellent thermo-physical properties and radiation hardness, isotropic graphite is presently the most promising material candidate for new high-power ion accelerators which will provide highest beam intensities and energies. Under these extreme conditions, specific accelerator components including production targets and beam protection modules are facing the risk of degradation due to radiation damage. Ion-beam induced damage effects were tested by irradiating polycrystalline, isotropic graphite samples at the UNILAC (GSI, Darmstadt) with 4.8 MeV per nucleon 132Xe, 150Sm, 197Au, and 238U ions applying fluences between 1 × 1011 and 1 × 1014 ions/cm2. The overall damage accumulation and its dependence on energy loss of the ions were studied by in situ 4-point resistivity measurements. With increasing fluence, the electric resistivity increases due to disordering of the graphitic structure. Irradiated samples were also analyzed off-line by means of micro-indentation in order to characterize mesoscale effects such as beam-induced hardening and stress fields within the specimen. With increasing fluence and energy loss, hardening becomes more pronounced.

Laser-induced thermo-lens in ion-implanted optically-transparent polymer

NASA Astrophysics Data System (ADS)

Stefanov, Ivan L.; Ivanov, Victor G.; Hadjichristov, Georgi B.

2009-10-01

A strong laser-induced thermo-lens (LITL) effect is found in optically-transparent ion-implanted polymer upon irradiation by a cw laser with a power up to 100 mW (λ = 532 nm). The effect is observed in bulk polymethylmethacrylate (PMMA) implanted with silicon ions (Si+). A series of PMMA specimens is examined, subjected to low-energy (50 keV) Si+ implantation at various dosages in the range from 1014 to 1017 ions/cm2. The thermo-lensing is unambiguously attributed to the modification of the subsurface region of the polymer upon the ion implantation. Having a gradient refractive-index in-depth profile, the subsurface organic-carbonaceous layer produced in the polymer by ion implantation, is responsible for the LITL effect observed in reflection geometry. The LITL occurs due to optical absorption of the ion-implanted layer of a thickness of about 100 nm buried in a depth ~ 100 nm, and subsequent laser-induced change in the refractive index of the Si+-implanted PMMA. Being of importance as considering photonic applications of ion-implanted optically-transparent polymers, the LITL effect in Si+-implanted PMMA is studied as a function of the implant dose, the incident laser power and incidence angle, and is linked to the structure formed in this ion-implanted plastic.

Enhanced light absorption of solar cells and photodetectors by diffraction

DOEpatents

Zaidi, Saleem H.; Gee, James M.

2005-02-22

Enhanced light absorption of solar cells and photodetectors by diffraction is described. Triangular, rectangular, and blazed subwavelength periodic structures are shown to improve performance of solar cells. Surface reflection can be tailored for either broadband, or narrow-band spectral absorption. Enhanced absorption is achieved by efficient optical coupling into obliquely propagating transmitted diffraction orders. Subwavelength one-dimensional structures are designed for polarization-dependent, wavelength-selective absorption in solar cells and photodetectors, while two-dimensional structures are designed for polarization-independent, wavelength-selective absorption therein. Suitable one and two-dimensional subwavelength periodic structures can also be designed for broadband spectral absorption in solar cells and photodetectors. If reactive ion etching (RIE) processes are used to form the grating, RIE-induced surface damage in subwavelength structures can be repaired by forming junctions using ion implantation methods. RIE-induced surface damage can also be removed by post RIE wet-chemical etching treatments.

Strategies to curb structural changes of lithium/transition metal oxide cathode materials & the changes’ effects on thermal & cycling stability

NASA Astrophysics Data System (ADS)

Xiqian, Yu; Enyuan, Hu; Seongmin, Bak; Yong-Ning, Zhou; Xiao-Qing, Yang

2016-01-01

Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. We also discuss applying the information about heat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue; it is widely accepted that the thermal instability of the cathodes is one of the most critical factors in thermal runaway and related safety problems. Project supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies (Grant No. DE-SC0012704).

The study on the electrical resistivity of Cu/V multilayer films subjected to helium (He) ion irradiation

NASA Astrophysics Data System (ADS)

Wang, P. P.; Xu, C.; Fu, E. G.; Du, J. L.; Gao, Y.; Wang, X. J.; Qiu, Y. H.

2018-05-01

Sputtering-deposited Cu/V multilayer films with the individual layer thickness varying from 2.5 nm to 100 nm were irradiated by 1 MeV helium (He) ion at the fluence of 6 ×1016 ions ·cm-2 at room temperature. The resistivity of Cu/V multilayer films after ion irradiation was evaluated as a function of individual layer thickness at 300 K and compared with their resistivity before ion irradiation. The results show that the resistivity change before and after ion irradiation is largely determined by the interface structure, grain boundary and radiation induced defects. A model amended based on the model used in describing the resistivity of as-deposited Cu/V multilayer films was proposed to describe the resistivity of ion irradiated Cu/V multilayer films by considering the point defects induced by ion irradiation, the effect of interface absorption on defects and the effect of interface microstructure in the multilayer films.

Mechanism of Formation of the Major Estradiol Product Ions Following Collisional Activation of the Molecular Anion in a Tandem Quadrupole Mass Spectrometer

NASA Astrophysics Data System (ADS)

Wooding, Kerry M.; Barkley, Robert M.; Hankin, Joseph A.; Johnson, Christopher A.; Bradford, Andrew P.; Santoro, Nanette; Murphy, Robert C.

2013-10-01

The importance of the mass spectral product ion structure is highlighted in quantitative assays, which typically use multiple reaction monitoring (MRM), and in the discovery of novel metabolites. Estradiol is an important sex steroid whose quantitation and metabolite identification using tandem mass spectrometry has been widely employed in numerous clinical studies. Negative electrospray ionization tandem mass spectrometry of estradiol (E2) results in several product ions, including the abundant m/z 183 and 169. Although m/z 183 is one of the most abundant product ions used in many quantitative assays, the structure of m/z 183 has not been rigorously examined. We suggest a structure for m/z 183 and a mechanism of formation consistent with collision induced dissociation (CID) of E2 and several stable isotopes ([D4]-E2, [13C6]-E2, and [D1]-E2). An additional product ion from E2, namely m/z 169, has also been examined. MS3 experiments indicated that both m/z 183 and m/z 169 originate from only E2 [M - H]- m/z 271. These ions, m/z 183 and m/z 169, were also present in the collision induced decomposition mass spectra of other prominent estrogens, estrone (E1) and estriol (E3), indicating that these two product ions could be used to elucidate the estrogenic origin of novel metabolites. We propose two fragmentation schemes to explain the CID data and suggest a structure of m/z 183 and m/z 169 consistent with several isotopic variants and high resolution mass spectrometric measurements.

Atypical behavior in the electron capture induced dissociation of biologically relevant transition metal ion complexes of the peptide hormone oxytocin

NASA Astrophysics Data System (ADS)

Kleinnijenhuis, Anne J.; Mihalca, Romulus; Heeren, Ron M. A.; Heck, Albert J. R.

2006-07-01

Doubly protonated ions of the disulfide bond containing nonapeptide hormone oxytocin and oxytocin complexes with different transition metal ions, that have biological relevance under physiological conditions, were subjected to electron capture dissociation (ECD) to probe their structural features in the gas phase. Although, all the ECD spectra were strikingly different, typical ECD behavior was observed for complexes of the nonapeptide hormone oxytocin with Ni2+, Co2+ and Zn2+, i.e., abundant c/z' and a'/y backbone cleavages and ECD characteristic S-S and S-C bond cleavages were observed. We propose that, although in the oxytocin-transition metal ion complexes the metal ions serve as the main initial capture site, the captured electron is transferred to other sites in the complex to form a hydrogen radical, which drives the subsequent typical ECD fragmentations. The complex of oxytocin with Cu2+ displayed noticeably different ECD behavior. The fragment ions were similar to fragment ions typically observed with low-energy collision induced dissociation (CID). We propose that the electrons captured by the oxytocin-Cu2+ complex might be favorably involved in reducing the Cu2+ metal ion to Cu+. Subsequent energy redistribution would explain the observed low-energy CID-type fragmentations. Electron capture resulted also in quite different specific cleavage sites for the complexes of oxytocin with Ni2+, Co2+ and Zn2+. This is an indication for structural differences in these complexes possibly linked to their significantly different biological effects on oxytocin-receptor binding, and suggests that ECD may be used to study subtle structural differences in transition metal ion-peptide complexes.

Memristive switching induced by 100 MeV Ag7+ ion irradiation in Ag/La0.7Sr0.3MnO3/Ag planar structures

NASA Astrophysics Data System (ADS)

Bhavsar, K. H.; Joshi, U. S.; Mistry, B. V.; Khan, S. A.; Avasthi, D. K.

2011-09-01

Resistive random access memory is one of the candidate technologies for the promising next generation non-volatile memories with fast switching speed, low power consumption and non-destructive readout. The swift heavy ion (SHI)-induced resistive switching behavior of Ag/La0.7Sr0.3MnO3/Ag planar structures, grown on SiO2 substrates by the chemical solution deposition technique, has been investigated. Five identical samples were irradiated by 100 MeV Ag7+ ions with fluence values ranging from 1×1011 to 5×1013 ions/cm2 at the Materials Science beamline of the IUAC, New Delhi. Upon irradiation, systematic amorphization and grain elongation was observed in the grazing incidence X-ray diffraction and atomic force microscopy, respectively. Four-terminal I-V curves indicate typical non-ohmic behavior of pristine Ag/La0.7Sr0.3MnO3/Ag planar geometry at room temperature for several voltage-sweeping cycles. On the other hand, well-defined hysteresis loops with sharp on-off transition in the I-V curves were observed for the sample irradiated with 100 MeV Ag7+ ions at 1×1012 ions/cm2, indicating that the sample possesses low resistance state and high resistance state. A symmetrical resistance ratio (R high/R low) of ∼ 330% at-1.7 V has been achieved. The resistance switching is bipolar and may be attributed to SHI-induced defects in the device. Such defect-induced resistive switching has recently been proposed theoretically, and our results are direct evidence of the phenomenon.

Origin of MeV ion irradiation-induced stress changes in SiO2

NASA Astrophysics Data System (ADS)

Brongersma, M. L.; Snoeks, E.; van Dillen, T.; Polman, A.

2000-07-01

The 4 MeV Xe ion irradiation of a thin thermally grown SiO2 film on a Si substrate leads to four different effects in which each manifests itself by a characteristic change in the mechanical stress state of the film: densification, ascribed to a beam-induced structural change in the silica network; stress relaxation by radiation-enhanced plastic flow; anisotropic expansion and stress generation; and transient stress relaxation ascribed to the annealing of point defects. Using sensitive wafer-curvature measurements, in situ measurements of the in-plane mechanical stress were made during and after ion irradiation at various temperatures in the range from 95 to 575 K, in order to study the magnitude of these effects, the mechanism behind them, as well as their interplay. It is found that the structural transformation leads to a state with an equilibrium density that is 1.7%-3.2% higher than the initial state, depending on the irradiation temperature. Due to the constraint imposed by the substrate, this transformation causes a tensile in-plane stress in the oxide film. This stress is relaxed by plastic flow, leading to densification of the film. The anisotropic strain-generation rate decreases linearly with temperature from (2.5±0.4)×10-17cm2/ion at 95 K to (-0.9±0.7)×10-17 cm2/ion at 575 K. The spectrum of irradiation-induced point defects, measured from the stress change after the ion beam was switched off, peaks below 0.23 eV and extends up to 0.80 eV. All four irradiation-induced effects can be described using a thermal spike model.

Structure-Functional Basis of Ion Transport in Sodium–Calcium Exchanger (NCX) Proteins

PubMed Central

Giladi, Moshe; Shor, Reut; Lisnyansky, Michal; Khananshvili, Daniel

2016-01-01

The membrane-bound sodium–calcium exchanger (NCX) proteins shape Ca2+ homeostasis in many cell types, thus participating in a wide range of physiological and pathological processes. Determination of the crystal structure of an archaeal NCX (NCX_Mj) paved the way for a thorough and systematic investigation of ion transport mechanisms in NCX proteins. Here, we review the data gathered from the X-ray crystallography, molecular dynamics simulations, hydrogen–deuterium exchange mass-spectrometry (HDX-MS), and ion-flux analyses of mutants. Strikingly, the apo NCX_Mj protein exhibits characteristic patterns in the local backbone dynamics at particular helix segments, thereby possessing characteristic HDX profiles, suggesting structure-dynamic preorganization (geometric arrangements of catalytic residues before the transition state) of conserved α1 and α2 repeats at ion-coordinating residues involved in transport activities. Moreover, dynamic preorganization of local structural entities in the apo protein predefines the status of ion-occlusion and transition states, even though Na+ or Ca2+ binding modifies the preceding backbone dynamics nearby functionally important residues. Future challenges include resolving the structural-dynamic determinants governing the ion selectivity, functional asymmetry and ion-induced alternating access. Taking into account the structural similarities of NCX_Mj with the other proteins belonging to the Ca2+/cation exchanger superfamily, the recent findings can significantly improve our understanding of ion transport mechanisms in NCX and similar proteins. PMID:27879668

Molecular mechanism of ATP binding and ion channel activation in P2X receptors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hattori, Motoyuki; Gouaux, Eric

P2X receptors are trimeric ATP-activated ion channels permeable to Na{sup +}, K{sup +} and Ca{sup 2+}. The seven P2X receptor subtypes are implicated in physiological processes that include modulation of synaptic transmission, contraction of smooth muscle, secretion of chemical transmitters and regulation of immune responses. Despite the importance of P2X receptors in cellular physiology, the three-dimensional composition of the ATP-binding site, the structural mechanism of ATP-dependent ion channel gating and the architecture of the open ion channel pore are unknown. Here we report the crystal structure of the zebrafish P2X4 receptor in complex with ATP and a new structure ofmore » the apo receptor. The agonist-bound structure reveals a previously unseen ATP-binding motif and an open ion channel pore. ATP binding induces cleft closure of the nucleotide-binding pocket, flexing of the lower body {beta}-sheet and a radial expansion of the extracellular vestibule. The structural widening of the extracellular vestibule is directly coupled to the opening of the ion channel pore by way of an iris-like expansion of the transmembrane helices. The structural delineation of the ATP-binding site and the ion channel pore, together with the conformational changes associated with ion channel gating, will stimulate development of new pharmacological agents.« less

Structure-Functional Basis of Ion Transport in Sodium-Calcium Exchanger (NCX) Proteins.

PubMed

Giladi, Moshe; Shor, Reut; Lisnyansky, Michal; Khananshvili, Daniel

2016-11-22

The membrane-bound sodium-calcium exchanger (NCX) proteins shape Ca 2+ homeostasis in many cell types, thus participating in a wide range of physiological and pathological processes. Determination of the crystal structure of an archaeal NCX (NCX_Mj) paved the way for a thorough and systematic investigation of ion transport mechanisms in NCX proteins. Here, we review the data gathered from the X-ray crystallography, molecular dynamics simulations, hydrogen-deuterium exchange mass-spectrometry (HDX-MS), and ion-flux analyses of mutants. Strikingly, the apo NCX_Mj protein exhibits characteristic patterns in the local backbone dynamics at particular helix segments, thereby possessing characteristic HDX profiles, suggesting structure-dynamic preorganization (geometric arrangements of catalytic residues before the transition state) of conserved α₁ and α₂ repeats at ion-coordinating residues involved in transport activities. Moreover, dynamic preorganization of local structural entities in the apo protein predefines the status of ion-occlusion and transition states, even though Na⁺ or Ca 2+ binding modifies the preceding backbone dynamics nearby functionally important residues. Future challenges include resolving the structural-dynamic determinants governing the ion selectivity, functional asymmetry and ion-induced alternating access. Taking into account the structural similarities of NCX_Mj with the other proteins belonging to the Ca 2+ /cation exchanger superfamily, the recent findings can significantly improve our understanding of ion transport mechanisms in NCX and similar proteins.

Understanding lattice defects to influence ferromagnetic order of ZnO nanoparticles by Ni, Cu, Ce ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Verma, Kuldeep Chand, E-mail: dkuldeep.physics@gmail.com; Kotnala, R.K., E-mail: rkkotnala@gmail.com

Future spintronics technologies based on diluted magnetic semiconductors (DMS) will rely heavily on a sound understanding of the microscopic origins of ferromagnetism in such materials. It remains unclear, however, whether the ferromagnetism in DMS is intrinsic - a precondition for spintronics - or due to dopant clustering. For this, we include a simultaneous doping from transition metal (Ni, Cu) and rare earth (Ce) ions in ZnO nanoparticles that increase the antiferromagnetic ordering to achieve high-T{sub c} ferromagnetism. Rietveld refinement of XRD patterns indicate that the dopant ions in ZnO had a wurtzite structure and the dopants, Ni{sup 2+}, Cu{sup 2+},more » Ce{sup 3+} ions, are highly influenced the lattice constants to induce lattice defects. The Ni, Cu, Ce ions in ZnO have nanoparticles formation than nanorods was observed in pure sample. FTIR involve some organic groups to induce lattice defects and the metal-oxygen bonding of Zn, Ni, Cu, Ce and O atoms to confirm wurtzite structure. Raman analysis evaluates the crystalline quality, structural disorder and defects in ZnO lattice with doping. Photoluminescence spectra have strong near-band-edge emission and visible emission bands responsible for defects due to oxygen vacancies. The energy band gap is calculated using Tauc relation. Room temperature ferromagnetism has been described due to bound magnetic polarons formation with Ni{sup 2+}, Cu{sup 2+}, Ce{sup 3+} ions in ZnO via oxygen vacancies. The zero field and field cooling SQUID measurement confirm the strength of antiferromagnetism in ZnO. The field cooling magnetization is studied by Curie-Weiss law that include antiferromagnetic interactions up to low temperature. The XPS spectra have involve +3/+4 oxidation states of Ce ions to influence the observed ferromagnetism. - Graphical abstract: The lattice defects/vacancies attributed by Ni and Ce ions in the wurtzite ZnO structure are responsible in high T{sub c} -ferromagnetism due to long-range magnetic interactions with cluster and spin-glass type growth. - Highlights: • Lattice defects/vacancies attributed high T{sub c} –ferromagnetism. • Transition metal and rare earth ions deform the wurtzite ZnO lattice to induce defects. • Oxygen vacancies are more favorable than Zn with Ni, Cu, Ce into ZnO. • Defects assisted long-range ferromagnetism of doped ZnO include cluster and spin-glass growth.« less

Stress influenced trapping processes in Si based multi-quantum well structures and heavy ions implanted Si

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ciurea, Magdalena Lidia, E-mail: ciurea@infim.ro; Lazanu, Sorina, E-mail: ciurea@infim.ro

2014-10-06

Multi-quantum well structures and Si wafers implanted with heavy iodine and bismuth ions are studied in order to evaluate the influence of stress on the parameters of trapping centers. The experimental method of thermostimullatedcurrents without applied bias is used, and the trapping centers are filled by illumination. By modeling the discharge curves, we found in multilayered structures the parameters of both 'normal' traps and 'stress-induced' ones, the last having a Gaussian-shaped temperature dependence of the cross section. The stress field due to the presence of stopped heavy ions implanted into Si was modeled by a permanent electric field. The increasemore » of the strain from the neighborhood of I ions to the neighborhood of Bi ions produces the broadening of some energy levels and also a temperature dependence of the cross sections for all levels.« less

Stress influenced trapping processes in Si based multi-quantum well structures and heavy ions implanted Si

NASA Astrophysics Data System (ADS)

Ciurea, Magdalena Lidia; Lazanu, Sorina

2014-10-01

Multi-quantum well structures and Si wafers implanted with heavy iodine and bismuth ions are studied in order to evaluate the influence of stress on the parameters of trapping centers. The experimental method of thermostimullatedcurrents without applied bias is used, and the trapping centers are filled by illumination. By modeling the discharge curves, we found in multilayered structures the parameters of both 'normal' traps and 'stress-induced' ones, the last having a Gaussian-shaped temperature dependence of the cross section. The stress field due to the presence of stopped heavy ions implanted into Si was modeled by a permanent electric field. The increase of the strain from the neighborhood of I ions to the neighborhood of Bi ions produces the broadening of some energy levels and also a temperature dependence of the cross sections for all levels.

Effect of silver ion-induced disorder on morphological, chemical and optical properties of poly (methyl methacrylate)

NASA Astrophysics Data System (ADS)

Arif, Shafaq; Saleemi, Farhat; Rafique, M. Shahid; Naab, Fabian; Toader, Ovidiu; Mahmood, Arshad; Aziz, Uzma

2016-11-01

Ion implantation is a versatile technique to tailor the surface properties of polymers in a controlled manner. In the present study, samples of poly (methyl methacrylate) (PMMA) have been implanted with 400 keV silver (Ag+) ion beam to various ion fluences ranging from 5 × 1013 to 5 × 1015 ions/cm2. The effect of Ag+ ion-induced disorder on morphological, chemical and optical properties of PMMA is analyzed using Atomic Force Microscope (AFM), Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy. Furthermore, the electrical conductivity of pristine and implanted PMMA is measured using four probe apparatus. The AFM images revealed the growth of nano-sized grainy structures and hillocks above the surface of implanted PMMA. The FTIR spectra confirmed the modifications in chemical structure of PMMA along with the formation of sbnd Cdbnd Csbnd carbon contents. The refractive index, extinction coefficient and photoconductivity of implanted PMMA have been found to increase as a function of ion fluence. Simultaneously, indirect optical band gap is reduced from 3.13 to 0.81 eV at a relatively high fluence (5 × 1015 ions/cm2). A linear correlation has been established between the band gap and Urbach energies. Moreover, the electrical conductivity of Ag+ implanted PMMA has increased from 2.14 × 10-10 (pristine) to 9.6 × 10-6 S/cm.

Electrospray ionization tandem mass spectrometry of ammonium cationized polyethers.

PubMed

Nasioudis, Andreas; Heeren, Ron M A; van Doormalen, Irene; de Wijs-Rot, Nicolette; van den Brink, Oscar F

2011-05-01

Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers. © American Society for Mass Spectrometry, 2011

Analysis of the electrolyte convection inside the concentration boundary layer during structured electrodeposition of copper in high magnetic gradient fields.

PubMed

König, Jörg; Tschulik, Kristina; Büttner, Lars; Uhlemann, Margitta; Czarske, Jürgen

2013-03-19

To experimentally reveal the correlation between electrodeposited structure and electrolyte convection induced inside the concentration boundary layer, a highly inhomogeneous magnetic field, generated by a magnetized Fe-wire, has been applied to an electrochemical system. The influence of Lorentz and magnetic field gradient force to the local transport phenomena of copper ions has been studied using a novel two-component laser Doppler velocity profile sensor. With this sensor, the electrolyte convection within 500 μm of a horizontally aligned cathode is presented. The electrode-normal two-component velocity profiles below the electrodeposited structure show that electrolyte convection is induced and directed toward the rim of the Fe-wire. The measured deposited structure directly correlates to the observed boundary layer flow. As the local concentration of Cu(2+) ions is enhanced due to the induced convection, maximum deposit thicknesses can be found at the rim of the Fe-wire. Furthermore, a complex boundary layer flow structure was determined, indicating that electrolyte convection of second order is induced. Moreover, the Lorentz force-driven convection rapidly vanishes, while the electrolyte convection induced by the magnetic field gradient force is preserved much longer. The progress for research is the first direct experimental proof of the electrolyte convection inside the concentration boundary layer that correlates to the deposited structure and reveals that the magnetic field gradient force is responsible for the observed structuring effect.

Dynamical ion transfer between coupled Coulomb crystals in a double-well potential.

PubMed

Klumpp, Andrea; Zampetaki, Alexandra; Schmelcher, Peter

2017-09-01

We investigate the nonequilibrium dynamics of coupled Coulomb crystals of different sizes trapped in a double well potential. The dynamics is induced by an instantaneous quench of the potential barrier separating the two crystals. Due to the intra- and intercrystal Coulomb interactions and the asymmetric population of the potential wells, we observe a complex reordering of ions within the two crystals as well as ion transfer processes from one well to the other. The study and analysis of the latter processes constitutes the main focus of this work. In particular, we examine the dependence of the observed ion transfers on the quench amplitude performing an analysis for different crystalline configurations ranging from one-dimensional ion chains via two-dimensional zigzag chains and ring structures to three-dimensional spherical structures. Such an analysis provides us with the means to extract the general principles governing the ion transfer dynamics and we gain some insight on the structural disorder caused by the quench of the barrier height.

Photoluminescent Au-Ge composite nanodots formation on SiO2 surface by ion induced dewetting

NASA Astrophysics Data System (ADS)

Datta, D. P.; Siva, V.; Singh, A.; Kanjilal, D.; Sahoo, P. K.

2017-09-01

Medium energy ion irradiation on a bilayer of Au and Ge on SiO2 is observed to result in gradual morphological evolution from an interconnected network to a nanodot array on the insulator surface. Structural and compositional analyses reveal composite nature of the nanodots, comprising of both Au and Ge. The growing nanostructures are found to be photoluminescent at room temperature where the emission intensity and wavelengths vary with morphology. The growth of such nanostructures can be understood in terms of dewetting of the metal layer under ion irradiation due to ion-induced melting along the ion tracks. The visible PL emission is found to be related with evolution of the Au-Ge nanodots. The study indicates a route towards single step synthesis of metal-semiconductor nanodots on insulator surface.

The capacity fading mechanism and improvement of cycling stability in MoS2-based anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Shu, Haibo; Li, Feng; Hu, Chenli; Liang, Pei; Cao, Dan; Chen, Xiaoshuang

2016-01-01

Two-dimensional (2D) layered MoS2 nanosheets possess great potential as anode materials for lithium ion batteries (LIBs), but they still suffer from poor cycling performance. Improving the cycling stability of electrode materials depends on a deep understanding of their dynamic structural evolution and reaction kinetics in the lithiation process. Herein, thermodynamic phase diagrams and the lithiation dynamics of MoS2-based nanostructures with the intercalation of lithium ions are studied by using first-principles calculations and ab initio molecular dynamics simulations. Our results demonstrate that the continuous intercalation of Li ions induces structural destruction of 2H phase MoS2 nanosheets in the discharge process that follows a layer-by-layer dissociation mechanism. Meanwhile, the intercalation of Li ions leads to a structural transition of MoS2 nanosheets from the 2H to the 1T phase due to the ultralow transition barriers (~0.1 eV). We find that the phase transition can slow down the dissociation of MoS2 nanosheets during lithiation. The result can be applied to explain extensive experimental observation of the fast capacity fading of MoS2-based anode materials between the first and the subsequent discharges. To suppress the dissociation of MoS2 nanosheets in the lithiation process, we propose a strategy by constructing a sandwich-like graphene/MoS2/graphene structure that indicates high chemical stability, superior conductivity, and high Li-ion mobility in the charge/discharge process, implying the possibility to induce an improvement in the anode cycling performance. This work opens a new route to rational design layered transition-metal disulfide (TMD) anode materials for LIBs with superior cycling stability and electrochemical performance.Two-dimensional (2D) layered MoS2 nanosheets possess great potential as anode materials for lithium ion batteries (LIBs), but they still suffer from poor cycling performance. Improving the cycling stability of electrode materials depends on a deep understanding of their dynamic structural evolution and reaction kinetics in the lithiation process. Herein, thermodynamic phase diagrams and the lithiation dynamics of MoS2-based nanostructures with the intercalation of lithium ions are studied by using first-principles calculations and ab initio molecular dynamics simulations. Our results demonstrate that the continuous intercalation of Li ions induces structural destruction of 2H phase MoS2 nanosheets in the discharge process that follows a layer-by-layer dissociation mechanism. Meanwhile, the intercalation of Li ions leads to a structural transition of MoS2 nanosheets from the 2H to the 1T phase due to the ultralow transition barriers (~0.1 eV). We find that the phase transition can slow down the dissociation of MoS2 nanosheets during lithiation. The result can be applied to explain extensive experimental observation of the fast capacity fading of MoS2-based anode materials between the first and the subsequent discharges. To suppress the dissociation of MoS2 nanosheets in the lithiation process, we propose a strategy by constructing a sandwich-like graphene/MoS2/graphene structure that indicates high chemical stability, superior conductivity, and high Li-ion mobility in the charge/discharge process, implying the possibility to induce an improvement in the anode cycling performance. This work opens a new route to rational design layered transition-metal disulfide (TMD) anode materials for LIBs with superior cycling stability and electrochemical performance. Electronic supplementary information (ESI) available: Models and energetics of Li adsorption/intercalation onto MoS2 sheets, details of the phase diagram calculations, schematic illustration for the structural evolution of lithiated MoS2 nanosheets, AIMD trajectories for lithiated silicene/MoS2/silicene composites, and movies for recording the AIMD simulation results. See DOI: 10.1039/c5nr07909h

Membrane Fusion Induced by Small Molecules and Ions

PubMed Central

Mondal Roy, Sutapa; Sarkar, Munna

2011-01-01

Membrane fusion is a key event in many biological processes. These processes are controlled by various fusogenic agents of which proteins and peptides from the principal group. The fusion process is characterized by three major steps, namely, inter membrane contact, lipid mixing forming the intermediate step, pore opening and finally mixing of inner contents of the cells/vesicles. These steps are governed by energy barriers, which need to be overcome to complete fusion. Structural reorganization of big molecules like proteins/peptides, supplies the required driving force to overcome the energy barrier of the different intermediate steps. Small molecules/ions do not share this advantage. Hence fusion induced by small molecules/ions is expected to be different from that induced by proteins/peptides. Although several reviews exist on membrane fusion, no recent review is devoted solely to small moleculs/ions induced membrane fusion. Here we intend to present, how a variety of small molecules/ions act as independent fusogens. The detailed mechanism of some are well understood but for many it is still an unanswered question. Clearer understanding of how a particular small molecule can control fusion will open up a vista to use these moleucles instead of proteins/peptides to induce fusion both in vivo and in vitro fusion processes. PMID:21660306

Hemin/G-quadruplex structure and activity alteration induced by magnesium cations.

PubMed

Kosman, J; Juskowiak, B

2016-04-01

The influence of metal cations on G-quadruplex structure and peroxidase-mimicking DNAzyme activity was investigated. Experiments revealed a significant role of magnesium ion, which in the presence of potassium cation influenced DNAzyme activity. This ability has been associated with alteration of G-quadruplex topology and consequently affinity to bind hemin molecule. It has been demonstrated that G-quadruplex based on PS2.M sequence under these conditions formed parallel topology, which exhibited lower activity than that observed in standard potassium-containing solution. On the other hand DNAzyme/magnesium ion system based on telomeric sequence, which did not undergo significant structural changes, exhibited higher peroxidase activity upon magnesium ion addition. In both cases, the stabilization effect of magnesium cations on G-quadruplex structure was observed. The mechanism of DNAzyme activity alteration by magnesium ion can be explained by its influence on the pKa value of DNAzyme. Magnesium ion decreased pKa for PS2.M based system but increased it for telomeric DNAzyme. Magnesium cation effect on G-quadruplex structure as well as DNAzyme activity is particularly important since this ion is one of the most common metal cations in biological samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Reversible Structural Swell-Shrink and Recoverable Optical Properties in Hybrid Inorganic-Organic Perovskite.

PubMed

Zhang, Yupeng; Wang, Yusheng; Xu, Zai-Quan; Liu, Jingying; Song, Jingchao; Xue, Yunzhou; Wang, Ziyu; Zheng, Jialu; Jiang, Liangcong; Zheng, Changxi; Huang, Fuzhi; Sun, Baoquan; Cheng, Yi-Bing; Bao, Qiaoliang

2016-07-26

Ion migration in hybrid organic-inorganic perovskites has been suggested to be an important factor for many unusual behaviors in perovskite-based optoelectronics, such as current-voltage hysteresis, low-frequency giant dielectric response, and the switchable photovoltaic effect. However, the role played by ion migration in the photoelectric conversion process of perovskites is still unclear. In this work, we provide microscale insights into the influence of ion migration on the microstructure, stability, and light-matter interaction in perovskite micro/nanowires by using spatially resolved optical characterization techniques. We observed that ion migration, especially the migration of MA(+) ions, will induce a reversible structural swell-shrink in perovskites and recoverably affect the reflective index, quantum efficiency, light-harvesting, and photoelectric properties. The maximum ion migration quantity in perovskites was as high as approximately 30%, resulting in lattice swell or shrink of approximately 4.4%. Meanwhile, the evidence shows that ion migration in perovskites could gradually accelerate the aging of perovskites because of lattice distortion in the reversible structural swell-shrink process. Knowledge regarding reversible structural swell-shrink and recoverable optical properties may shed light on the development of optoelectronic and converse piezoelectric devices based on perovskites.

Modelling and Holographic Visualization of Space Radiation-Induced DNA Damage

NASA Technical Reports Server (NTRS)

Plante, Ianik

2017-01-01

Space radiation is composed by a mixture of ions of different energies. Among these, heavy inos are of particular importance because their health effects are poorly understood. In. the recent years, a software named RITRACKS (Relativistic Ion Tracks) was developed to simulate the detailed radiation track structure, several DNA models and DNA damage. As the DNA structure is complex due to packing, it is difficult to the damage using a regular computer screen.

Electrically Active Defects In Solar Cells Based On Amorphous Silicon/Crystalline Silicon Heterojunction After Irradiation By Heavy Xe Ions

NASA Astrophysics Data System (ADS)

Harmatha, Ladislav; Mikolášek, Miroslav; Stuchlíková, L'ubica; Kósa, Arpád; Žiška, Milan; Hrubčín, Ladislav; Skuratov, Vladimir A.

2015-11-01

The contribution is focused on the diagnostics of structures with a heterojunction between amorphous and crystalline silicon prepared by HIT (Heterojunction with an Intrinsic Thin layer) technology. The samples were irradiated by Xe ions with energy 167 MeV and doses from 5 × 108 cm-2 to 5 × 1010 cm-2. Radiation defects induced in the bulk of Si and at the hydrogenated amorphous silicon and crystalline silicon (a-Si:H/c-Si) interface were identified by Deep Level Transient Spectroscopy (DLTS). Radiation induced A-centre traps, boron vacancy traps and different types of divacancies with a high value of activation energy were observed. With an increased fluence of heavy ions the nature and density of the radiation induced defects was changed.

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction

PubMed Central

Yoshimatsu, K.; Niwa, M.; Mashiko, H.; Oshima, T.; Ohtomo, A.

2015-01-01

Transition metal oxides display various electronic and magnetic phases such as high-temperature superconductivity. Controlling such exotic properties by applying an external field is one of the biggest continuous challenges in condensed matter physics. Here, we demonstrate clear superconductor-insulator transition of LiTi2O4 films induced by Li-ion electrochemical reaction. A compact electrochemical cell of pseudo-Li-ion battery structure is formed with a superconducting LiTi2O4 film as an anode. Li content in the film is controlled by applying a constant redox voltage. An insulating state is achieved by Li-ion intercalation to the superconducting film by applying reduction potential. In contrast, the superconducting state is reproduced by applying oxidation potential to the Li-ion intercalated film. Moreover, superconducting transition temperature is also recovered after a number of cycles of Li-ion electrochemical reactions. This complete reversible transition originates in difference in potentials required for deintercalation of initially contained and electrochemically intercalated Li+ ions. PMID:26541508

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction.

PubMed

Yoshimatsu, K; Niwa, M; Mashiko, H; Oshima, T; Ohtomo, A

2015-11-06

Transition metal oxides display various electronic and magnetic phases such as high-temperature superconductivity. Controlling such exotic properties by applying an external field is one of the biggest continuous challenges in condensed matter physics. Here, we demonstrate clear superconductor-insulator transition of LiTi2O4 films induced by Li-ion electrochemical reaction. A compact electrochemical cell of pseudo-Li-ion battery structure is formed with a superconducting LiTi2O4 film as an anode. Li content in the film is controlled by applying a constant redox voltage. An insulating state is achieved by Li-ion intercalation to the superconducting film by applying reduction potential. In contrast, the superconducting state is reproduced by applying oxidation potential to the Li-ion intercalated film. Moreover, superconducting transition temperature is also recovered after a number of cycles of Li-ion electrochemical reactions. This complete reversible transition originates in difference in potentials required for deintercalation of initially contained and electrochemically intercalated Li(+) ions.

Evidence for Sequence Scrambling and Divergent H/D Exchange Reactions of Doubly-Charged Isobaric b-Type Fragment Ions

NASA Astrophysics Data System (ADS)

Zekavat, Behrooz; Miladi, Mahsan; Al-Fdeilat, Abdullah H.; Somogyi, Arpad; Solouki, Touradj

2014-02-01

To date, only a limited number of reports are available on structural variants of multiply-charged b-fragment ions. We report on observed bimodal gas-phase hydrogen/deuterium exchange (HDX) reaction kinetics and patterns for substance P b10 2+ that point to presence of isomeric structures. We also compare HDX reactions, post-ion mobility/collision-induced dissociation (post-IM/CID), and sustained off-resonance irradiation-collision induced dissociation (SORI-CID) of substance P b10 2+ and a cyclic peptide with an identical amino acid (AA) sequence order to substance P b10. The observed HDX patterns and reaction kinetics and SORI-CID pattern for the doubly charged head-to-tail cyclized peptide were different from either of the presumed isomers of substance P b10 2+, suggesting that b10 2+ may not exist exclusively as a head-to-tail cyclized structure. Ultra-high mass measurement accuracy was used to assign identities of the observed SORI-CID fragment ions of substance P b10 2+; over 30 % of the observed SORI-CID fragment ions from substance P b10 2+ had rearranged (scrambled) AA sequences. Moreover, post-IM/CID experiments revealed the presence of two conformer types for substance P b10 2+, whereas only one conformer type was observed for the head-to-tail cyclized peptide. We also show that AA sequence scrambling from CID of doubly-charged b-fragment ions is not unique to substance P b10 2+.

Evidence for sequence scrambling and divergent H/D exchange reactions of doubly-charged isobaric b-type fragment ions.

PubMed

Zekavat, Behrooz; Miladi, Mahsan; Al-Fdeilat, Abdullah H; Somogyi, Arpad; Solouki, Touradj

2014-02-01

To date, only a limited number of reports are available on structural variants of multiply-charged b-fragment ions. We report on observed bimodal gas-phase hydrogen/deuterium exchange (HDX) reaction kinetics and patterns for substance P b10(2+) that point to presence of isomeric structures. We also compare HDX reactions, post-ion mobility/collision-induced dissociation (post-IM/CID), and sustained off-resonance irradiation-collision induced dissociation (SORI-CID) of substance P b10(2+) and a cyclic peptide with an identical amino acid (AA) sequence order to substance P b10. The observed HDX patterns and reaction kinetics and SORI-CID pattern for the doubly charged head-to-tail cyclized peptide were different from either of the presumed isomers of substance P b10(2+), suggesting that b10(2+) may not exist exclusively as a head-to-tail cyclized structure. Ultra-high mass measurement accuracy was used to assign identities of the observed SORI-CID fragment ions of substance P b10(2+); over 30% of the observed SORI-CID fragment ions from substance P b10(2+) had rearranged (scrambled) AA sequences. Moreover, post-IM/CID experiments revealed the presence of two conformer types for substance P b10(2+), whereas only one conformer type was observed for the head-to-tail cyclized peptide. We also show that AA sequence scrambling from CID of doubly-charged b-fragment ions is not unique to substance P b10(2+).

Communication: Gas-phase structural isomer identification by Coulomb explosion of aligned molecules

NASA Astrophysics Data System (ADS)

Burt, Michael; Amini, Kasra; Lee, Jason W. L.; Christiansen, Lars; Johansen, Rasmus R.; Kobayashi, Yuki; Pickering, James D.; Vallance, Claire; Brouard, Mark; Stapelfeldt, Henrik

2018-03-01

The gas-phase structures of four difluoroiodobenzene and two dihydroxybromobenzene isomers were identified by correlating the emission angles of atomic fragment ions created, following femtosecond laser-induced Coulomb explosion. The structural determinations were facilitated by confining the most polarizable axis of each molecule to the detection plane prior to the Coulomb explosion event using one-dimensional laser-induced adiabatic alignment. For a molecular target consisting of two difluoroiodobenzene isomers, each constituent structure could additionally be singled out and distinguished.

Study of irradiation induced surface pattern and structural changes in Inconel 718 alloy

NASA Astrophysics Data System (ADS)

Wan, Hao; Si, Naichao; Zhao, Zhenjiang; Wang, Jian; Zhang, Yifei

2018-05-01

Helium ions irradiation induced surface pattern and structural changes of Inconel 718 alloy were studied with the combined utilization of atomic force microscopy (AFM), x-ray diffraction (XRD) and transmission electron microscopy (TEM). In addition, SRIM-2013 software was used to calculate the sputtering yield and detailed collision events. The result shows that, irradiation dose play an important role in altering the pattern of the surface. Enhanced irradiation aggravated the surface etching and increased the surface roughness. In ion irradiated layer, large amount of interstitials, vacancies and defect sinks were produced. Moreover, in samples with increasing dose irradiation, the dependence of interplanar spacing variation due to point defects clustering on sink density was discussed.

In-operando high-speed tomography of lithium-ion batteries during thermal runaway

PubMed Central

Finegan, Donal P.; Scheel, Mario; Robinson, James B.; Tjaden, Bernhard; Hunt, Ian; Mason, Thomas J.; Millichamp, Jason; Di Michiel, Marco; Offer, Gregory J.; Hinds, Gareth; Brett, Dan J.L.; Shearing, Paul R.

2015-01-01

Prevention and mitigation of thermal runaway presents one of the greatest challenges for the safe operation of lithium-ion batteries. Here, we demonstrate for the first time the application of high-speed synchrotron X-ray computed tomography and radiography, in conjunction with thermal imaging, to track the evolution of internal structural damage and thermal behaviour during initiation and propagation of thermal runaway in lithium-ion batteries. This diagnostic approach is applied to commercial lithium-ion batteries (LG 18650 NMC cells), yielding insights into key degradation modes including gas-induced delamination, electrode layer collapse and propagation of structural degradation. It is envisaged that the use of these techniques will lead to major improvements in the design of Li-ion batteries and their safety features. PMID:25919582

Magnetic and topographical modifications of amorphous Co-Fe thin films induced by high energy Ag7+ ion irradiation

NASA Astrophysics Data System (ADS)

Pookat, G.; Hysen, T.; Al-Harthi, S. H.; Al-Omari, I. A.; Lisha, R.; Avasthi, D. K.; Anantharaman, M. R.

2013-09-01

We have investigated the effects of swift heavy ion irradiation on thermally evaporated 44 nm thick, amorphous Co77Fe23 thin films on silicon substrates using 100 MeV Ag7+ ions fluences of 1 × 1011 ions/cm2, 1 × 1012 ions/cm2, 1 × 1013 ions/cm2, and 3 × 1013 ions/cm2. The structural modifications upon swift heavy irradiation were investigated using glancing angle X-ray diffraction. The surface morphological evolution of thin film with irradiation was studied using Atomic Force Microscopy. Power spectral density analysis was used to correlate the roughness variation with structural modifications investigated using X-ray diffraction. Magnetic measurements were carried out using vibrating sample magnetometry and the observed variation in coercivity of the irradiated films is explained on the basis of stress relaxation. Magnetic force microscopy images are subjected to analysis using the scanning probe image processor software. These results are in agreement with the results obtained using vibrating sample magnetometry. The magnetic and structural properties are correlated.

Development of nano-fabrication technique utilizing self-organizational behavior of point defects induced by ion irradiation

NASA Astrophysics Data System (ADS)

Nitta, Noriko; Taniwaki, Masafumi

2006-04-01

The present authors proposed a novel nano-fabrication technique that is able to arrange the fine cells orderly, based on their finding in GaSb implanted at a low temperature. In this article, first the experimental results that anomalous cellular structure was formed in GaSb by ion implantation is introduced and the self-organizational formation mechanism of the structure is described. Next a nano-fabrication technique that utilizes focused ion beam is described. This technique consists of two procedures, i.e. the formation process of the voids array and the development of the initial array to ordered cellular structure. Finally, the nano-fabrication is actually performed by this technique and their results are reported. Fabrication succeeded in structures where the dot (cell) interval was 100 nm or larger. The minimum ion dose for initial voids which develops to the ordered cellular structure is evaluated. It is also shown that the substrate temperature during implantation is an essential parameter for this technique.

Shock-wave structure in a partially ionized gas

NASA Technical Reports Server (NTRS)

Lu, C. S.; Huang, A. B.

1974-01-01

The structure of a steady plane shock in a partially ionized gas has been investigated using the Boltzmann equation with a kinetic model as the governing equation and the discrete ordinate method as a tool. The effects of the electric field induced by the charge separation on the shock structure have also been studied. Although the three species of an ionized gas travel with approximately the same macroscopic velocity, the individual distribution functions are found to be very different. In a strong shock the atom distribution function may have double peaks, while the ion distribution function has only one peak. Electrons are heated up much earlier than ions and atoms in a partially ionized gas. Because the interactions of electrons with atoms and with ions are different, the ion temperature can be different from the atom temperature.

Simulation of radiation damage in minerals by sequential ion irradiations

NASA Astrophysics Data System (ADS)

Nakasuga, W. M.; Li, W.; Ewing, R. C.

2015-12-01

Radiation effects due to α-decay of U and Th and spontaneous fission of 238U control the production and recovery of the radiation-induced structure of minerals, as well as the diffusion of elements through the mineral host. However, details of how the damage microstructure is produced and annealed remain unknown. Our recent ion beam experiments demonstrate that ionizing radiation from the α-particle recovers the damage structure. Thus, the damage structure is not only the result of the thermal hisotry of the sample, but also of the complex interaction between ionizing and ballistic damage mechanisms. By combining ion irradiations with transmission electron microscopy (TEM), we have simulated the damage produced by α-decay and fission. The α-particle induced annealing has been simulated by in situ TEM observation of consecutive ion-irradiations: i.) 1 MeV Kr2+ (simulating 70 keV α-recoils induced damage), ii.) followed by 400 keV He+ (simulating 4.5 MeV α-particle induced annealing). Thus, in addition to the well-established effects of thermal annealing, the α-particle annealing effects, as evidenced by partical recrystallization of the originally, fully-amorphous apatite upon the α-particle irriadations, should also be considered when evaluating diffusion and release of elements, such as He. In addition, the fission track annealing has been simulated by a new sample preparation method that allows for direct observation of radiation damage recovery at each point along the length of latent tracks created by 80 MeV Xe ions (a typical fission fragment). The initial, rapid reduction in etched track length during isothermal annealing is explained by the rapid annealing of those sections of the track with smaller diameters, as observed directly by in situ TEM. In summary, the atomic-scale investigation of radiation damage in minerals is critical to understanding of the influence of raidation damage on diffusion and kinetics that are fundamental to geochronology.

Charge-induced geometrical reorganization of DNA oligonucleotides studied by tandem mass spectrometry and ion mobility.

PubMed

Ickert, Stefanie; Hofmann, Johanna; Riedel, Jens; Beck, Sebastian; Pagel, Kevin; Linscheid, Michael W

2018-04-01

Mass spectrometry is applied as a tool for the elucidation of molecular structures. This premises that gas-phase structures reflect the original geometry of the analytes, while it requires a thorough understanding and investigation of the forces controlling and affecting the gas-phase structures. However, only little is known about conformational changes of oligonucleotides in the gas phase. In this study, a series of multiply charged DNA oligonucleotides (n = 15-40) has been subjected to a comprehensive tandem mass spectrometric study to unravel transitions between different ionic gas-phase structures. The nucleobase sequence and the chain length were varied to gain insights into their influence on the geometrical oligonucleotide organization. Altogether, 23 oligonucleotides were analyzed using collision-induced fragmentation. All sequences showed comparable correlation regarding the characteristic collision energy. This value that is also a measure for stability, strongly correlates with the net charge density of the precursor ions. With decreasing charge of the oligonucleotides, an increase in the fragmentation energy was observed. At a distinct charge density, a deviation from linearity was observed for all studied species, indicating a structural reorganization. To corroborate the proposed geometrical change, collisional cross-sections of the oligonucleotides at different charge states were determined using ion mobility-mass spectrometry. The results clearly indicate that an increase in charge density and thus Coulomb repulsion results in the transition from a folded, compact form to elongated structures of the precursor ions. Our data show this structural transition to depend mainly on the charge density, whereas sequence and size do not have an influence.

MALDI Q-TOF CID MS for Diagnostic Ion Screening of Human Milk Oligosaccharide Samples

PubMed Central

Jovanović, Marko; Tyldesley-Worster, Richard; Pohlentz, Gottfried; Peter-Katalinić, Jasna

2014-01-01

Human milk oligosaccharides (HMO) represent the bioactive components of human milk, influencing the infant’s gastrointestinal microflora and immune system. Structurally, they represent a highly complex class of analyte, where the main core oligosaccharide structures are built from galactose and N-acetylglucosamine, linked by 1–3 or 1–4 glycosidic linkages and potentially modified with fucose and sialic acid residues. The core structures can be linear or branched. Additional structural complexity in samples can be induced by endogenous exoglycosidase activity or chemical procedures during the sample preparation. Here, we show that using matrix-assisted laser desorption/ionization (MALDI) quadrupole-time-of-flight (Q-TOF) collision-induced dissociation (CID) as a fast screening method, diagnostic structural information about single oligosaccharide components present in a complex mixture can be obtained. According to sequencing data on 14 out of 22 parent ions detected in a single high molecular weight oligosaccharide chromatographic fraction, 20 different oligosaccharide structure types, corresponding to over 30 isomeric oligosaccharide structures and over 100 possible HMO isomers when biosynthetic linkage variations were taken into account, were postulated. For MS/MS data analysis, we used the de novo sequencing approach using diagnostic ion analysis on reduced oligosaccharides by following known biosynthetic rules. Using this approach, de novo characterization has been achieved also for the structures, which could not have been predicted. PMID:24743894

Combining Structural Probes in the Gas Phase - Ion Mobility- Resolved Action-FRET

NASA Astrophysics Data System (ADS)

Daly, Steven; MacAleese, Luke; Dugourd, Philippe; Chirot, Fabien

2018-01-01

In the context of native mass spectrometry, the development of gas-phase structural probes sensitive to the different levels of structuration of biomolecular assemblies is necessary to push forward conformational studies. In this paper, we provide the first example of the combination of ion mobility (IM) and Förster resonance energy transfer (FRET) measurements within the same experimental setup. The possibility to obtain mass- and mobility-resolved FRET measurements is demonstrated on a model peptide and applied to monitor the collision-induced unfolding of ubiquitin. [Figure not available: see fulltext.

Response of Gd 2 Ti 2 O 7 and La 2 Ti 2 O 7 to swift-heavy ion irradiation and annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Sulgiye; Lang, Maik; Tracy, Cameron L.

2015-07-01

Swift heavy ion (2 GeV 181Ta) irradiation-induced amorphization and temperature-induced recrystallization of cubic pyrochlore Gd2Ti2O7 (Fd3¯m) are compared with the response of a compositionally-similar material with a monoclinic-layered perovskite-type structure, La2Ti2O7 (P21). The averaged electronic energy loss, dE/dx, was 37 keV/nm and 35 keV/nm in Gd2Ti2O7 and La2Ti2O7, respectively. Systematic analysis of the structural modifications was completed using transmission electron microscopy, synchrotron X-ray diffraction, Raman spectroscopy, and small-angle X-ray scattering. Increasing ion-induced amorphization with increasing ion fluence was evident in the X-ray diffraction patterns of both compositions by a reduction in the intensity of the diffraction maxima concurrent with themore » growth in intensity of a broad diffuse scattering halo. Transmission electron microscopy analysis showed complete amorphization within ion tracks (diameter: ~10 nm) for the perovskite-type material; whereas a concentric, core–shell morphology was evident in the ion tracks of the pyrochlore, with an outer shell of disordered yet still crystalline material with the fluorite structure surrounding an amorphous track core (diameter: ~9 nm). The radiation response of both titanate oxides with the same stoichiometry can be understood in terms of differences in their structures and compositions. While the radiation damage susceptibility of pyrochlore A2B2O7 materials decreases as a function of the cation radius ratio rA/rB, the current study correlates this behavior with the stability field of monoclinic structures, where rLa/rTi > rGd/rTi. Isochronal annealing experiments of the irradiated materials showed complete recrystallization of La2Ti2O7 at 775 °C and of Gd2Ti2O7 at 850 °C. The annealing behavior is discussed in terms of enhanced damage recovery in La2Ti2O7, compared to the pyrochlore compounds Gd2Ti2O7. The difference in the recrystallization behavior may be related to structural constraints, i.e., reconstructing a low symmetry versus a high symmetry phase.« less

Xenon-ion-induced and thermal mixing of Co/Si bilayers and their interplay

NASA Astrophysics Data System (ADS)

Novaković, M.; Zhang, K.; Popović, M.; Bibić, N.; Hofsäss, H.; Lieb, K. P.

2011-05-01

Studies on ion-irradiated transition-metal/silicon bilayers demonstrate that interface mixing and silicide phase formation depend sensitively on the ion and film parameters, including the structure of the metal/Si interface. Thin Co layers e-gun evaporated to a thickness of 50 nm on Si(1 0 0) wafers were bombarded at room temperature with 400-keV Xe + ions at fluences of up to 3 × 10 16 cm -2. We used either crystalline or pre-amorphized Si wafers the latter ones prepared by 1.0-keV Ar-ion implantation. The as-deposited or Xe-ion-irradiated samples were then isochronally annealed at temperatures up to 700 °C. Changes of the bilayer structures induced by ion irradiation and/or annealing were investigated with RBS, XRD and HRTEM. The mixing rate for the Co/c-Si couples, Δ σ2/ Φ = 3.0(4) nm 4, is higher than the value expected for ballistic mixing and about half the value typical for spike mixing. Mixing of pre-amorphized Si is much weaker relative to crystalline Si wafers, contrary to previous results obtained for Fe/Si bilayers. Annealing of irradiated samples produces very similar interdiffusion and phase formation patterns above 400 °C as in the non-irradiated Co/Si bilayers: the phase evolution follows the sequence Co 2Si → CoSi → CoSi 2.

Effect of rapid thermal annealing on nanocrystalline TiO2 thin films synthesized by swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Thakurdesai, Madhavi; Kanjilal, D.; Bhattacharyya, Varsha

2012-08-01

Irradiation by swift heavy ions (SHI) is unique tool to synthesize nanocrystalline thin films. We have reported transformation of 100 nm thick amorphous films into nanocrystalline film due to irradiation by 100 MeV Ag ion beam. Oblate shaped nanoparticles having anatase phase of TiO2 were formed on the surface of the irradiated films. In the present investigation, these films are annealed at 350 °C for 2 min in oxygen atmosphere by Rapid Thermal Annealing (RTA) method. During RTA processing, the temperature rises abruptly and this thermal instability is expected to alter surface morphology, structural and optical properties of nanocrystalline TiO2 thin films. Thus in the present work, effect of RTA on SHI induced nanocrystalline thin films of TiO2 is studied. The effect of RTA processing on the shape and size of TiO2 nanoparticles is studied by Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Glancing Angle X-ray Diffraction (GAXRD) studies are carried to investigate structural changes induced by RTA processing. Optical characterization is carried out by UV-vis spectroscopy and photoluminescence (PL) spectroscopy. The changes observed in structural and optical properties of nanocrystalline TiO2 thin films after RTA processing are attributed to the annihilation of SHI induced defects.

Low energy ion beam induced changes in ETFE polymer

NASA Astrophysics Data System (ADS)

Parada, M. A.; Delalez, N.; de Almeida, A.; Muntele, C.; Muntele, I.; Ila, D.

2006-01-01

Low energy ion beam bombardment of ethylenetetrafluoroethylene (ETFE) modifies the physical and chemical properties of the polymer surface in ways that enhance or compromise applications in the technological and medical physics fields. When a material is exposed to ionizing radiation, its changes depends on the type, energy and intensity of the applied radiation. In order to determine the nature of the induced radiation changes, ETFE films were bombarded with fluences from 1012 up to 1015 ions/cm2 of keV N and protons. The emission of gaseous species during the bombardments was monitored with a residual gas analyser (RGA). The bombarded films were analysed with optical absorption photospectrometry (OAP), Fourier transform infrared (FTIR) and micro-Raman spectrometries that determine the chemical nature of the structural changes caused by ions bombardment.

Ion induced millimetre-scale structures growth on metal surfaces

NASA Astrophysics Data System (ADS)

Girka, O.; Bizyukov, O.; Balkova, Y.; Myroshnyk, M.; Bizyukov, I.; Bogatyrenko, S.

2018-04-01

Polished polycrystalline Plansee tungsten (W) sample with purity 99.99 wt% and 0.75 mm thickness has been exposed to intense argon (Ar) ion beam with average energy of 2 keV and etched through in the centre. As a result, castle-like structures with strong asymmetry and with the height of >200 μm have been formed. Structures can be observed by naked eyes and with scanning-electron microscopy (SEM). It has been revealed, that the structures have been formed not immediately, but at the later stages of irradiation. Primary factors favouring the formation for the structures are relaxation of the surface stresses and activated surface mobility of atoms.

Nanofabrication with a helium ion microscope

NASA Astrophysics Data System (ADS)

Maas, Diederik; van Veldhoven, Emile; Chen, Ping; Sidorkin, Vadim; Salemink, Huub; van der Drift, Emile..; Alkemade, Paul

2010-03-01

The recently introduced helium ion microscope (HIM) is capable of imaging and fabrication of nanostructures thanks to its sub-nanometer sized ion probe. The unique interaction of the helium ions with the sample material provides very localized secondary electron emission, thus providing a valuable signal for high-resolution imaging as well as a mechanism for very precise nanofabrication. The low proximity effects, due to the low yield of backscattered ions and the confinement of the forward scattered ions into a narrow cone, enable patterning of ultra-dense sub-10 nm structures. This paper presents various nanofabrication results obtained with direct-write, with scanning helium ion beam lithography, and with helium ion beam induced deposition.

Optimization of a low noise detection circuit for probing the structure of damage cascades with IBIC

DOE PAGES

Auden, Elizabeth C.; Doyle, Barney L.; Bielejec, Edward; ...

2015-06-18

Optimal detector / pre-amplifier combinations have been identified for the use of light ion IBIC (ion beam induced charge) to probe the physical structure of electrically active defects in damage cascades caused by heavy ion implantation. The ideal detector must have a sufficiently thin dead layer that incident ions will produce the majority of damage cascades in the depletion region of the detector rather than the dead layer. Detector and circuit noise must be low enough to detect the implantation of a single heavy ion as well as the decrease in the light ion IBIC signal caused by Shockley-Read-Hall recombinationmore » when the beam scans regions of the detector damaged by the heavy ion. The IBIC signals from three detectors irradiated with 750 keV He⁺ ions are measured with commercial and bespoke charge sensitive pre-amplifiers to identify the combination with the lowest noise.« less

Structure and mechanisms underlying ion transport in ternary polymer electrolytes containing ionic liquids

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2017-02-01

We use all atom molecular dynamics simulations to investigate the influence of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) ionic liquid on the structure and transport properties of poly(ethylene oxide) (PEO) polymer electrolytes doped with LiPF6 salt. We observe enhanced diffusivities of the Li+, PF6-, and BMIM+ ions with increasing loading of the ionic liquid. Interplay between the different ion-ion and ion-polymer interactions is seen to lead to a destabilization of the Li-PF6 coordination and increase in the strength of association between the Li+ cations and the polymer backbone. As a consequence, the polymer segmental relaxation times are shown to be only moderately affected by the addition of ionic liquids. The ionic-liquid induced changes in the mobilities of Li+ ions are seen to be correlated to polymer segmental relaxation times. However, the mobilities of BMIM+ ions are seen to be more strongly correlated to the BMIM-PF6 ion-pair relaxation times.

Spatial structure of ion beams in an expanding plasma

NASA Astrophysics Data System (ADS)

Aguirre, E. M.; Scime, E. E.; Thompson, D. S.; Good, T. N.

2017-12-01

We report spatially resolved perpendicular and parallel, to the magnetic field, ion velocity distribution function (IVDF) measurements in an expanding argon helicon plasma. The parallel IVDFs, obtained through laser induced fluorescence (LIF), show an ion beam with v ≈ 8000 m/s flowing downstream and confined to the center of the discharge. The ion beam is measurable for tens of centimeters along the expansion axis before the LIF signal fades, likely a result of metastable quenching of the beam ions. The parallel ion beam velocity slows in agreement with expectations for the measured parallel electric field. The perpendicular IVDFs show an ion population with a radially outward flow that increases with distance from the plasma axis. Structures aligned to the expanding magnetic field appear in the DC electric field, the electron temperature, and the plasma density in the plasma plume. These measurements demonstrate that at least two-dimensional and perhaps fully three-dimensional models are needed to accurately describe the spontaneous acceleration of ion beams in expanding plasmas.

Chromosomal intrachanges induced by swift iron ions

NASA Astrophysics Data System (ADS)

Horstmann, M.; Durante, M.; Johannes, C.; Obe, G.

We measured the induction of structural aberrations in human chromosome 5 induced by iron ions using the novel technique of multicolor banding in situ hybridization (mBAND). Human lymphocytes isolated from whole blood were exposed in vitro to 500 MeV/n (LET = 200 keV/μm, doses 1 or 4 Gy) Fe nuclei at the HIMAC accelerator in Chiba (Japan). Chromosomes were prematurely condensed by calyculin A after 48 h in culture and slides were painted by mBAND. We found a frequency of 0.11 and 0.57 residual breakpoints per chromosome 5 after 1 and 4 Gy Fe-ions, respectively. Inter-chromosomal exchanges were the prevalent aberration type measured at both doses, followed by terminal deletions, and by intra-chromosomal exchanges. Among intra-chromosomal exchanges, intra-arm events were more frequent than inter-arm, but a significant number of intra-changes was associated to inter-changes involving the same chromosome after 4 Gy of iron ions. These events show that the complexity of chromosomal exchanges induced by heavy ions can be higher than expected by previous FISH studies.

Radiation-induced amorphization of Langasite La3Ga5SiO14

NASA Astrophysics Data System (ADS)

Yao, Tiankai; Lu, Fengyuan; Zhang, Haifeng; Gong, Bowen; Ji, Wei; Zuo, Lei; Lian, Jie

2018-03-01

Single crystals of Langasite La3Ga5SiO14 (LGS) were irradiated by 1 MeV Kr2+ ions at temperature range from 298 to 898 K in order to simulate the damage effect of neutron radiation on Langasite, a candidate sensor material proposed as high temperature and pressure sensors in nuclear reactors. The microstructure evolution of LGS as functions of irradiation dose and temperature was followed by in-situ TEM observation through electron diffraction pattern. LGS is found to be sensitive to ion beam irradiation-induced amorphization from displacive heavy ions with a low critical dose of ∼0.5 ± 0.2 dpa (neutron fluence of (1.6 ± 0.6) × 1019 neutrons/cm2) at room temperature. The critical amorphization temperature, Tc, is determined to be 910 ± 10 K. Under simultaneous ionizing electron (300 keV, 45 nA) and displacive heavy ion irradiations (1-MeV Kr2+ and flux of 6.25 × 1011 ions/cm2·s), LGS displayed greater stability of crystal structure against amorphization, possibly due to the electron radiation-induced recovery of displacive damage by heavy ions.

Investigation of collision-induced dissociation products and structures of gas-phase [ M·GlyGlyHis-H]+ ( M = Fe, Ni, Cu, and Zn) complexes.

PubMed

Gannamani, Bharathi; Shin, Joong-Won

2017-02-01

Collision-induced dissociation is carried out for electrosprayed [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , [Cu·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + complexes. [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + yield metal-bound peptide sequence ions and dehydrated ions as primary products, whereas [Cu·GlyGlyHis-H] + generates a more extensive series of metal-bound sequence ions and a product arising from the unusual loss of a formaldehyde moiety; dehydration is significantly suppressed for this complex. Density functional theory calculations show that the copper ion-deprotonated peptide binding energy is substantially higher than those in other complexes, suggesting that there is a correlation between ion-ligand binding energy and their fragmentation behavior.

The Structure of the Metal Transporter Tp34 and its Affinity for Divalent Metal Ions

NASA Astrophysics Data System (ADS)

Knutsen, Gregory; Deka, Ranjit; Brautigam, Chad; Tomchick, Diana; Machius, Mischa; Norgard, Michael

2007-10-01

Tp34 is periplasmic membrane protein of the nonculitvatable spirochete Treponema pallidum, the pathogen of syphillis. It was proposed that Tp34 is a divalent metal transporter, but the identity of the preferred metal ion(s) was unclear. In this study we investigated the ability of divalent metal ions to induce rTp34 dimerization using hydrodynamic techniques and determine the crystal structure of metal bound forms. Using analytical ultracentrifugation sedimentation velocity experiments, we determined that cobalt is superior to nickel at inducing the dimerization of rTp34. rTp34 was crystallized and selected crystals were incubated at a pH 7.5 with CuSO4 and NiSO4. Diffraction experiments were conducted and the processed electron density maps showed that copper was bound to the major metal binding site as well as to three additional minor binding sites. By contrast nickel was only bound to the major metal binding site in one monomer and to three additional minor sites. These results along with previous findings support evidence of Tp34 being involved with metal transport and/or iron utilization.

Structural Transformation of Guanine Coordination Motifs in Water Induced by Metal ions and Temperature.

PubMed

Li, Wei; Jin, Jing; Liu, Xiaoqing; Wang, Li

2018-06-15

The transformation effects of metal ions and temperature on the DNA bases guanine (G) metal-organic coordination motifs in water have been investigated by scanning tunneling microcopy (STM). The G molecules form an ordered hydrogen-bonded structure at the water- highly oriented pyrolytic graphite (HOPG) interface. The STM observations reveal that the canonical G/9H form can be transformed into the G/(3H, 7H) tautomer by increasing the temperature of the G solution to 38.6oC. Moreover, metal ions bind with G molecules to form G4Fe13+, G3Fe32+ and the heterochiral intermixed G4Na1+ metal-organic networks after the introduction of the alkali-metal ions in cellular environment.

Heavy ion irradiation effects of brannerite-type ceramics

NASA Astrophysics Data System (ADS)

Lian, J.; Wang, L. M.; Lumpkin, G. R.; Ewing, R. C.

2002-05-01

Brannerite, UTi 2O 6, occurs in polyphase Ti-based, crystalline ceramics that are under development for plutonium immobilization. In order to investigate radiation effects caused by α-decay events of Pu, a 1 MeV Kr + irradiation on UTi 2O 6, ThTi 2O 6, CeTi 2O 6 and a more complex material, composed of Ca-containing brannerite and pyrochlore, was performed over a temperature range of 25-1020 K. The ion irradiation-induced crystalline-to-amorphous transformation was observed in all brannerite samples. The critical amorphization temperatures of the different brannerite compositions are: 970 K, UTi 2O 6; 990 K, ThTi 2O 6; 1020 K, CeTi 2O 6. The systematic increase in radiation resistance from Ce-, Th- to U-brannerite is related to the difference of mean atomic mass of A-site cation in the structure. As compared with the pyrochlore structure-type, brannerite phases are more susceptible to ion irradiation-induced amorphization. The effects of structure and chemical compositions on radiation resistance of brannerite-type and pyrochlore-type ceramics are discussed.

Study of novel junctionless Ge n-Tunneling Field-Effect Transistors with lightly doped drain (LDD) region

NASA Astrophysics Data System (ADS)

Liu, Xiangyu; Hu, Huiyong; Wang, Bin; Wang, Meng; Han, Genquan; Cui, Shimin; Zhang, Heming

2017-02-01

In this paper, a novel junctionless Ge n-Tunneling Field-Effect Transistors (TFET) structure is proposed. The simulation results show that Ion = 5.5 × 10-5A/μm is achieved. The junctionless device structure enhances Ion effectively and increases the region where significant BTBT occurs, comparing with the normal Ge-nTEFT. The impact of the lightly doped drain (LDD) region is investigated. A comparison of Ion and Ioff of the junctionless Ge n-TFET with different channel doping concentration ND and LDD doping concentration NLDD is studied. Ioff is reduced 1 order of magnitude with the optimized ND and NLDD are 1 × 1018cm-3 and 1 × 1017 cm-3, respectively. To reduce the gate induced drain leakage (GIDL) current, the impact of the sloped gate oxide structure is also studied. By employing the sloped gate oxide structure, the below 60 mV/decade subthreshold swing S = 46.2 mV/decade is achieved at Ion = 4.05 × 10-5A/μm and Ion/Ioff = 5.7 × 106.

Oxygen Ion Energization at Mars: Comparison of MAVEN and Mars Express Observations to Global Hybrid Simulation

NASA Astrophysics Data System (ADS)

Jarvinen, R.; Brain, D. A.; Modolo, R.; Fedorov, A.; Holmström, M.

2018-02-01

We study oxygen ion energization in the Mars-solar wind interaction by comparing particle and magnetic field observations on the Mars Atmosphere and Volatile EvolutioN (MAVEN) and Mars Express missions to a global hybrid simulation. We find that large-scale structures of the Martian-induced magnetosphere and plasma environment as well as the Mars heavy ion plume as seen by multispacecraft observations are reproduced by the model. Using the simulation, we estimate the dynamics of escaping oxygen ions by analyzing their distance and time of flight as a function of the gained kinetic energy along spacecraft trajectories. In the upstream region the heavy ion energization resembles single-particle solar wind ion pickup acceleration as expected, while within the induced magnetosphere the energization displays other features including the heavy ion plume from the ionosphere. Oxygen ions take up to 80 s and travel the distance of 20,000 km after their emission from the ionosphere to the induced magnetosphere or photoionization from the neutral exosphere before they have reached energies of 10 keV in the plume along the analyzed spacecraft orbits. Lower oxygen ion energies of 100 eV are reached faster in 10-20 s over the distance of 100-200 km in the plume. Our finding suggests that oxygen ions are typically observed within the first half of their gyrophase if the spacecraft periapsis is on the hemisphere where the solar wind convection electric field points away from Mars.

Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO 2.5-σ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qinghua; He, Xu; Shi, Jinan

Oxygen ion transport is the key issue in redox processes. Visualizing the process of oxygen ion migration with atomic resolution is highly desirable for designing novel devices such as oxidation catalysts, oxygen permeation membranes, and solid oxide fuel cells. We show the process of electrically induced oxygen migration and subsequent reconstructive structural transformation in a SrCoO 2.5-σ film by scanning transmission electron microscopy. We find that the extraction of oxygen from every second SrO layer occurs gradually under an electrical bias; beyond a critical voltage, the brownmillerite units collapse abruptly and evolve into a periodic nano-twined phase with a highmore » c/a ratio and distorted tetrahedra. These results show that oxygen vacancy rows are not only natural oxygen diffusion channels, but also preferred sites for the induced oxygen vacancies. These direct experimental results of oxygen migration may provide a common mechanism for the electrically induced structural evolution of oxides.« less

Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO 2.5-σ

DOE PAGES

Zhang, Qinghua; He, Xu; Shi, Jinan; ...

2017-07-24

Oxygen ion transport is the key issue in redox processes. Visualizing the process of oxygen ion migration with atomic resolution is highly desirable for designing novel devices such as oxidation catalysts, oxygen permeation membranes, and solid oxide fuel cells. We show the process of electrically induced oxygen migration and subsequent reconstructive structural transformation in a SrCoO 2.5-σ film by scanning transmission electron microscopy. We find that the extraction of oxygen from every second SrO layer occurs gradually under an electrical bias; beyond a critical voltage, the brownmillerite units collapse abruptly and evolve into a periodic nano-twined phase with a highmore » c/a ratio and distorted tetrahedra. These results show that oxygen vacancy rows are not only natural oxygen diffusion channels, but also preferred sites for the induced oxygen vacancies. These direct experimental results of oxygen migration may provide a common mechanism for the electrically induced structural evolution of oxides.« less

Electronic and crystal structure changes induced by in-plane oxygen vacancies in multiferroic YMnO 3

DOE PAGES

Cheng, Shaobo; Meng, Qingping; Li, Mengli; ...

2016-02-08

Here, the widely spread oxygen vacancies (V O) in multiferroic materials can strongly affect their physical properties. However, their exact influence has rarely been identified in hexagonal manganites. Here, with the combined use of transmission electron microscopy (TEM) and first-principles calculations, we have systematically studied the electronic and crystal structure modifications induced by V O located at the same Mn atomic plane (in-plane V O). Our TEM experiments reveal that the easily formed in-plane V O not only influence the electronic structure of YMnO 3 but alter the in-plane Wyckoff positions of Mn ions, which may subsequently affect the intraplanemore » and interplane exchange interaction of Mn ions. The ferroelectricity is also impaired due to the introduction of V O. Further calculations confirm these electronic and structural changes and modifications. Our results indicate that the electronic and crystal structure of YMnO 3 can be manipulated by the creation of V O.« less

Morphological transformations in the magnetite biomineralizing protein Mms6 in iron solutions: A small-angle x-ray scattering study

DOE PAGES

Zhang, Honghu; Liu, Xunpei; Feng, Shuren; ...

2015-02-10

In this study, magnetotactic bacteria that produce magnetic nanocrystals of uniform size and well-defined morphologies have inspired the use of biomineralization protein Mms6 to promote formation of uniform magnetic nanocrystals in vitro. Small angle X-ray scattering (SAXS) studies in physiological solutions reveal that Mms6 forms compact globular three-dimensional (3D) micelles (approximately 10 nm in diameter) that are, to a large extent, independent of concentration. In the presence of iron ions in the solutions, the general micellar morphology is preserved, however, with associations among micelles that are induced by iron ions. Compared with Mms6, the m2Mms6 mutant (with the sequence ofmore » hydroxyl/carboxyl containing residues in the C-terminal domain shuffled) exhibits subtle morphological changes in the presence of iron ions in solutions. The analysis of the SAXS data is consistent with a hierarchical core–corona micellar structure similar to that found in amphiphilic polymers. The addition of ferric and ferrous iron ions to the protein solution induces morphological changes in the micellar structure by transforming the 3D micelles into objects of reduced dimensionality of 2, with fractal-like characteristics (including Gaussian-chain-like) or, alternatively, platelet-like structures.« less

How Does CeIII Nitrate Dissolve in a Protic Ionic Liquid? A Combined Molecular Dynamics and EXAFS Study.

PubMed

Serva, Alessandra; Migliorati, Valentina; Spezia, Riccardo; D'Angelo, Paola

2017-06-22

A diluted solution of Ce(NO 3 ) 3 in the protic ionic liquid (IL) ethylammonium nitrate (EAN) was investigated using molecular dynamics (MD) simulations and extended X-ray absorption fine structure (EXAFS) spectroscopy. For the first time polarizable effects were included in the MD force field to describe a heavy metal ion in a protic IL, but, unlike water, they were found to be unessential. The Ce III ion first solvation shell is formed by nitrate ions arranged in an icosahedral structure, and an equilibrium between monodentate and bidentate ligands is present in the solution. By combining distance and angular distribution functions it was possible to unambiguously identify this peculiar coordination geometry around the ions dissolved in solution. The metal ions are solvated within the polar domains of the EAN nanostructure and the dissolved salt induces almost no reorganization of the pre-existing structure of EAN upon solubilization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular dynamics study of structural damage in amorphous silica induced by swift heavy-ion radiation

NASA Astrophysics Data System (ADS)

Zhen, J. S.; Yang, Q.; Yan, Y. H.; Jiang, X. W.; Yan, S. A.; Chen, W.; Guo, X. Q.

2016-03-01

In this paper, the radiation defects induced by the swift heavy ions and the recoil atoms in amorphous SiO2 were studied. The energy of recoil atoms induced by the incident Au ions in SiO2 was calculated by using Monte Carlo method. Results show that the average energies of recoils reach the maximum (200 eV for Si and 130 eV for O, respectively) when the incident energy of Au ion is 100 MeV. Using Tersoff/zbl potential with the newly built parameters, the defects formation processes in SiO2 induced by the recoils were studied by using molecular dynamics method. The displacement threshold energies (Ed) for Si and O atoms are found to be 33.5 and 16.3 eV, respectively. Several types of under- and over-coordinated Si and O defects were analyzed. The results demonstrate that Si3, Si5, and O1 are the mainly defects in SiO2 after radiation. Besides, the size of cylindrical damage region produced by a single recoil atom was calculated. The calculation shows that the depth and the radius are up to 2.0 and 1.4 nm when the energy of recoils is 200 eV. Finally, it is estimated that the Au ion would induce a defected track with a diameter of 4 nm in SiO2.

FTIR spectroscopy structural analysis of the interaction between Lactobacillus kefir S-layers and metal ions

NASA Astrophysics Data System (ADS)

Gerbino, E.; Mobili, P.; Tymczyszyn, E.; Fausto, R.; Gómez-Zavaglia, A.

2011-02-01

FTIR spectroscopy was used to structurally characterize the interaction of S-layer proteins extracted from two strains of Lactobacillus kefir (the aggregating CIDCA 8348 and the non-aggregating JCM 5818) with metal ions (Cd +2, Zn +2, Pb +2 and Ni +2). The infrared spectra indicate that the metal/protein interaction occurs mainly through the carboxylate groups of the side chains of Asp and Glut residues, with some contribution of the NH groups belonging to the peptide backbone. The frequency separation between the νCOO - anti-symmetric and symmetric stretching vibrations in the spectra of the S-layers in presence of the metal ions was found to be ca. 190 cm -1 for S-layer CIDCA 8348 and ca. 170 cm -1 for JCM 5818, denoting an unidentate coordination in both cases. Changes in the secondary structures of the S-layers induced by the interaction with the metal ions were also noticed: a general trend to increase the amount of β-sheet structures and to reduce the amount of α-helices was observed. These changes allow the proteins to adjust their structure to the presence of the metal ions at minimum energy expense, and accordingly, these adjustments were found to be more important for the bigger ions.

Enhancement of Curie temperature of barium hexaferrite by dense electronic excitations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Manju; Kashyap, Subhash C.; Gupta, Hem C.

2014-07-15

Curie temperature of polycrystalline barium hexaferrite (BaFe{sub 12}O{sub 19}), prepared by conventional solid state technique, is anomalously and significantly enhanced (by nearly 15%) by energetic heavy ion irradiation (150 MeV, Ag{sup 12+}) at ambient temperature due to dense electronic excitations Moderate fluence (1 × 10{sup 12} ions/cm{sup 2}) induces structural defects giving rise to above enhancement. As established by X-ray diffraction, scanning electron microscopy and Raman studies, higher fluence (1 × 10{sup 13} ions/cm{sup 2}) has structurally transformed the sample to amorphous phase with marginal change in magnetization and Curie temperature.

SHI irradiation effect on pure and Mn doped ZnO thin films

NASA Astrophysics Data System (ADS)

Khawal, H. A.; Raskar, N. D.; Dole, B. N.

2017-05-01

Investigated the structural, surface, electrical and modifications induced by Swift Heavy Ions (SHI) irradiation on pure and Mn substituted ZnO thin films were observed. Thin films of Zn1-xMnxO (x = 0.00, 0.04) were synthesized using the dip coating technique. All thin films irradiated by Li3+ swift heavy ions with fluence 5 × 1013 ions/cm2. The XRD peak reveals that all the samples exhibit wurtzite structures. Surface morphology of samples was investigated by SEM, it was observed that pristine samples of ZnO thin film shows spherical shape but for 4 % Mn substituted ZnO thin film with 5 × 1013 ions/cm2 fluence, it reveals that big grain spherical morphology like structure respectively. I-V characteristics were recorded in the voltage range -5 to 5 V. All curves were passed through origin and nearly linear exhibit ohmic in nature for the films.

Structuring of material parameters in lithium niobate crystals with low-mass, high-energy ion radiation

NASA Astrophysics Data System (ADS)

Peithmann, K.; Eversheim, P.-D.; Goetze, J.; Haaks, M.; Hattermann, H.; Haubrich, S.; Hinterberger, F.; Jentjens, L.; Mader, W.; Raeth, N. L.; Schmid, H.; Zamani-Meymian, M.-R.; Maier, K.

2011-10-01

Ferroelectric lithium niobate crystals offer a great potential for applications in modern optics. To provide powerful optical components, tailoring of key material parameters, especially of the refractive index n and the ferroelectric domain landscape, is required. Irradiation of lithium niobate crystals with accelerated ions causes strong structured modifications in the material. The effects induced by low-mass, high-energy ions (such as 3He with 41 MeV, which are not implanted, but transmit through the entire crystal volume) are reviewed. Irradiation yields large changes of the refractive index Δn, improved domain engineering capability within the material along the ion track, and waveguiding structures. The periodic modification of Δn as well as the formation of periodically poled lithium niobate (PPLN) (supported by radiation damage) is described. Two-step knock-on displacement processes, 3He→Nb and 3He→O causing thermal spikes, are identified as origin for the material modifications.

Metal Ion Binding at the Catalytic Site Induces Widely Distributed Changes in a Sequence Specific Protein–DNA Complex

PubMed Central

2016-01-01

Metal ion cofactors can alter the energetics and specificity of sequence specific protein–DNA interactions, but it is unknown if the underlying effects on structure and dynamics are local or dispersed throughout the protein–DNA complex. This work uses EcoRV endonuclease as a model, and catalytically inactive lanthanide ions, which replace the Mg2+ cofactor. Nuclear magnetic resonance (NMR) titrations indicate that four Lu3+ or two La3+ cations bind, and two new crystal structures confirm that Lu3+ binding is confined to the active sites. NMR spectra show that the metal-free EcoRV complex with cognate (GATATC) DNA is structurally distinct from the nonspecific complex, and that metal ion binding sites are not assembled in the nonspecific complex. NMR chemical shift perturbations were determined for 1H–15N amide resonances, for 1H–13C Ile-δ-CH3 resonances, and for stereospecifically assigned Leu-δ-CH3 and Val-γ-CH3 resonances. Many chemical shifts throughout the cognate complex are unperturbed, so metal binding does not induce major conformational changes. However, some large perturbations of amide and side chain methyl resonances occur as far as 34 Å from the metal ions. Concerted changes in specific residues imply that local effects of metal binding are propagated via a β-sheet and an α-helix. Both amide and methyl resonance perturbations indicate changes in the interface between subunits of the EcoRV homodimer. Bound metal ions also affect amide hydrogen exchange rates for distant residues, including a distant subdomain that contacts DNA phosphates and promotes DNA bending, showing that metal ions in the active sites, which relieve electrostatic repulsion between protein and DNA, cause changes in slow dynamics throughout the complex. PMID:27786446

Structural dependence of flavonoid interactions with Cu2+ ions: implications for their antioxidant properties.

PubMed Central

Brown, J E; Khodr, H; Hider, R C; Rice-Evans, C A

1998-01-01

The flavonoids constitute a large group of polyphenolic phytochemicals with antioxidant properties in vitro. The interactions of four structurally related flavonoids (quercetin, kaempferol, rutin and luteolin) with Cu2+ ions were investigated in terms of the extent to which they undergo complex formation through chelation or modification through oxidation, as well as in their structural dependence. The ortho 3',4'-dihydroxy substitution in the B ring is shown to be important for Cu2+-chelate formation, thereby influencing the antioxidant activity. The presence of a 3-hydroxy group in the flavonoid structure enhances the oxidation of quercetin and kaempferol, whereas luteolin and rutin, each lacking the 3-hydroxy group, do not oxidize as readily in the presence of Cu2+ ions. The results also demonstrate that the reactivities of the flavonoids in protecting low-density lipoprotein (LDL) against Cu2+ ion-induced oxidation are dependent on their structural properties in terms of the response of the particular flavonoid to Cu2+ ions, whether chelation or oxidation, their partitioning abilities between the aqueous compartment and the lipophilic environment within the LDL particle, and their hydrogen-donating antioxidant properties. PMID:9494082

Crystal structure of human glycine receptor-α3 bound to antagonist strychnine.

PubMed

Huang, Xin; Chen, Hao; Michelsen, Klaus; Schneider, Stephen; Shaffer, Paul L

2015-10-08

Neurotransmitter-gated ion channels of the Cys-loop receptor family are essential mediators of fast neurotransmission throughout the nervous system and are implicated in many neurological disorders. Available X-ray structures of prokaryotic and eukaryotic Cys-loop receptors provide tremendous insights into the binding of agonists, the subsequent opening of the ion channel, and the mechanism of channel activation. Yet the mechanism of inactivation by antagonists remains unknown. Here we present a 3.0 Å X-ray structure of the human glycine receptor-α3 homopentamer in complex with a high affinity, high-specificity antagonist, strychnine. Our structure allows us to explore in detail the molecular recognition of antagonists. Comparisons with previous structures reveal a mechanism for antagonist-induced inactivation of Cys-loop receptors, involving an expansion of the orthosteric binding site in the extracellular domain that is coupled to closure of the ion pore in the transmembrane domain.

Double-ring structure formation of intense ion beams with finite radius in a pre-formed plasma

NASA Astrophysics Data System (ADS)

Hu, Zhang-Hu; Wang, Xiao-Juan; Zhao, Yong-Tao; Wang, You-Nian

2017-12-01

The dynamic structure evolution of intense ion beams with a large edge density gradient is investigated in detail with an analytical model and two-dimensional particle-in-cell (PIC) simulations, with special attention paid to the influence of beam radius. At the initial stage of beam-plasma interactions, the ring structure is formed due to the transverse focusing magnetic field induced by the unneutralized beam current in the beam edge region. As the beam-plasma system evolves self-consistently, a second ring structure appears in the case of ion beams with a radius much larger than the plasma skin depth, due to the polarity change in the transverse magnetic field in the central regions compared with the outer, focusing field. Influences of the current-filamentation and two-stream instability on the ring structure can be clearly observed in PIC simulations by constructing two different simulation planes.

Non-ideal operating conditions of the ion source prototype for the ITER neutral beam injector due to thermal deformation of the support structure.

PubMed

Sartori, E; Pavei, M; Marcuzzi, D; Zaccaria, P

2014-02-01

The beam formation and acceleration of the ITER neutral beam injector will be studied in the full-scale ion source, Source for Production of Ions of Deuterium Extracted from a RF plasma (SPIDER). It will be able to sustain 40 A deuterium ion beam during 1-h pulses. The operating conditions of its multi-aperture electrodes will diverge from ideality, as a consequence of inhomogeneous heating and thermally induced deformations in the support structure of the extraction and acceleration grids, which operate at different temperatures. Meeting the requirements on the aperture alignment and distance between the grids with such a large number of apertures (1280) and the huge support structures constitute a challenge. Examination of the structure thermal deformation in transient and steady conditions has been carried out, evaluating their effect on the beam performance: the paper describes the analyses and the solutions proposed to mitigate detrimental effects.

Self-induced steady-state magnetic field in the negative ion sources with localized rf power deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shivarova, A.; Todorov, D., E-mail: dimitar-tdrv@phys.uni-sofia-bg; Lishev, St.

2016-02-15

The study is in the scope of a recent activity on modeling of SPIDER (Source for Production of Ions of Deuterium Extracted from RF plasma) which is under development regarding the neutral beam injection heating system of ITER. The regime of non-ambipolarity in the source, established before, is completed here by introducing in the model the steady state magnetic field, self-induced in the discharge due to the dc current flowing in it. Strong changes in the discharge structure are reported.

Thermal annealing and SHI irradiation induced modifications in sandwiched structured Carbon-gold-Carbon (a-C/Au/a-C) nanocomposite thin film

NASA Astrophysics Data System (ADS)

Singh, S. K.; Singhal, R.

2017-09-01

In the present work, we study the annealing and swift heavy ion (SHI) beam induced modifications in the optical and structural properties of sandwiched structured Carbon-gold-Carbon (a-C/Au/a-C) nanocomposite (NCs) thin films. The NCs thin films were synthesized by electron-beam evaporation technique at room temperature with ∼30 nm thickness for both carbon layer and ∼6 nm for gold layer. Gold-carbon NCs thin films were annealed in the presence of argon at a temperature of 500 °C, 600 °C and 750 °C. The NCs thin films were also irradiated with 90 MeV Ni ions beam with different ion fluences in the range from 3 × 1012, 6 × 1012 and 1 × 1013 ions/cm2. Surface plasmon resonance (SPR) of Au nanoparticles are not observed in the pristine film but, after annealing at temperature of 600 °C and 750 °C, it was clearly seen at ∼534 nm as confirmed by UV-visible absorption spectroscopy. 90 MeV Ni irradiated thin film at the fluence of 1 × 1013 ions/cm2 also show strong absorption band at ∼534 nm. The growth and size of Au nanoparticle for pristine and 90 MeV Ni ion irradiated thin film with fluence of 1 × 1013 ions/cm2, were estimated by Transmission electron microscopy (TEM) images with the bi-model distribution. The size of the gold nanoparticle (NPs) was found to be ∼4.5 nm for the pristine film and ∼5.4 nm for the irradiated film at a fluence of 1 × 1013 ions/cm2. The thickness and metal atomic fraction in carbon matrix were estimated by Rutherford backscattering spectroscopy (RBS). The effect of annealing as well as heavy ion irradiation on D and G band of carbon matrix were studied by Raman spectroscopy.

Investigating ion channel conformational changes using voltage clamp fluorometry.

PubMed

Talwar, Sahil; Lynch, Joseph W

2015-11-01

Ion channels are membrane proteins whose functions are governed by conformational changes. The widespread distribution of ion channels, coupled with their involvement in most physiological and pathological processes and their importance as therapeutic targets, renders the elucidation of these conformational mechanisms highly compelling from a drug discovery perspective. Thanks to recent advances in structural biology techniques, we now have high-resolution static molecular structures for members of the major ion channel families. However, major questions remain to be resolved about the conformational states that ion channels adopt during activation, drug modulation and desensitization. Patch-clamp electrophysiology has long been used to define ion channel conformational states based on functional criteria. It achieves this by monitoring conformational changes at the channel gate and cannot detect conformational changes occurring in regions distant from the gate. Voltage clamp fluorometry involves labelling cysteines introduced into domains of interest with environmentally sensitive fluorophores and inferring structural rearrangements from voltage or ligand-induced fluorescence changes. Ion channel currents are monitored simultaneously to verify the conformational status. By defining real time conformational changes in domains distant from the gate, this technique provides unexpected new insights into ion channel structure and function. This review aims to summarise the methodology and highlight recent innovative applications of this powerful technique. This article is part of the Special Issue entitled 'Fluorescent Tools in Neuropharmacology'. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Biological Effectiveness of Accelerated Particles for the Induction of Chromosome Damage: Track Structure Effects and Cytogenetic Signatures of High-LET Exposure

NASA Technical Reports Server (NTRS)

George, K.; Hada, M.; Chappell, L.; Cucinotta, F. A.

2012-01-01

Track structure models predict that at a fixed value of LET, particles with lower charge number, Z will have a higher biological effectiveness compared to particles with a higher Z. In this report we investigated how track structure effects induction of chromosomal aberration in human cells. Human lymphocytes were irradiated in vitro with various energies of accelerated iron, silicon, neon, or titanium ions and chromosome damage was assessed in using three color FISH chromosome painting in chemically induced PCC samples collected a first cell division post irradiation. The LET values for these ions ranged from 30 to 195 keV/micrometers. Of the particles studied, Neon ions have the highest biological effectiveness for induction of total chromosome damage, which is consistent with track structure model predictions. For complex-type exchanges 64 MeV/ u Neon and 450 MeV/u Iron were equally effective and induced the most complex damage. In addition we present data on chromosomes exchanges induced by six different energies of protons (5 MeV/u to 2.5 GeV/u). The linear dose response term was similar for all energies of protons suggesting that the effect of the higher LET at low proton energies is balanced by the production of nuclear secondaries from the high energy protons. All energies of protons have a much higher percentage of complex-type chromosome exchanges than gamma rays, signifying a cytogenetic signature for proton exposures.

Effect of structural transformation of C+-ion implanted PMMA into quasi-continuous carbonaceous layer on its optical and electrical properties

NASA Astrophysics Data System (ADS)

Arif, Shafaq; Rafique, M. Shahid; Saleemi, Farhat; Sagheer, Riffat

2018-02-01

The samples of Polymethylmethacrylate (PMMA) have been implanted with 500 keV C+-ions at different ion fluences ranging from 9.3 × 1013 to 8.4 × 1014 ions/cm2. The structural modifications are examined by Fourier Transform Infrared and Raman spectral studies. For the investigation of optical, electrical and surface morphological properties of implanted samples UV-Visible spectrometer, four probe apparatus and optical microscope have been employed. The FTIR spectra confirmed the cleavage of chemicals bonds as a consequence of polymer chain scission, whereas, Raman studies revealed the transformation of PMMA structure into quasi-continuous amorphous carbon with increasing ion fluences. A continuous reduction has been observed in the optical band gap of PMMA from 3.16 to 1.42 eV. Moreover, the refractive index, extinction coefficient and electrical conductivity of implanted PMMA are found to be an increasing function of the ion fluence. The micrographic images revealed the signatures of ion-induced defects like cracking, dehydrogenation, stress and swelling on the surface of PMMA. These implanted samples have a potential to be used in the field of optical communications and thin plastic flexible electronics.

Strain-induced structural defects and their effects on the electrochemical performances of silicon core/germanium shell nanowire heterostructures

DOE PAGES

Lin, Yung-Chen; Kim, Dongheun; Li, Zhen; ...

2016-12-14

Here we report on strain-induced structural defect formation in core Si nanowire of Si/Ge core/shell nanowire heterostructure and influences of the structural defects on the electrochemical performances in lithium-ion battery anodes based on Si/Ge core/shell nanowire heterostructures. The induced structural defects consisting of stacking faults and dislocations in the core Si nanowire were observed for the first time. The generation of stacking faults in Si/Ge core/shell nanowire heterostructure is observed to prefer settling in either only Ge shell region or in both Ge shell and Si core regions and is associated with the increase of the shell volume fraction. Themore » relax of misfit strain in [112] oriented core/shell nanowire heterostructure leads to subsequent gliding of Shockley partial dislocations, preferentially forming the twins. The observation of cross-over defect formation is of great importance for the understanding of heteroepitaxy in radial heterostructures at nanoscale and building the three dimensional heterostructures for the various applications. In addition, the effect of the defect formation on nanomaterial’s functionality is investigated by electrochemical performance test. The Si/Ge core/shell nanowire heterostructures enhance the gravimetric capacity of lithium ion battery anodes under fast charging/discharging rates compared to Si nanowires. However, the induced structural defects hamper lithiation of the Si/Ge core/shell nanowire heterostructure.« less

Strain-induced structural defects and their effects on the electrochemical performances of silicon core/germanium shell nanowire heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yung-Chen; Kim, Dongheun; Li, Zhen

Here we report on strain-induced structural defect formation in core Si nanowire of Si/Ge core/shell nanowire heterostructure and influences of the structural defects on the electrochemical performances in lithium-ion battery anodes based on Si/Ge core/shell nanowire heterostructures. The induced structural defects consisting of stacking faults and dislocations in the core Si nanowire were observed for the first time. The generation of stacking faults in Si/Ge core/shell nanowire heterostructure is observed to prefer settling in either only Ge shell region or in both Ge shell and Si core regions and is associated with the increase of the shell volume fraction. Themore » relax of misfit strain in [112] oriented core/shell nanowire heterostructure leads to subsequent gliding of Shockley partial dislocations, preferentially forming the twins. The observation of cross-over defect formation is of great importance for the understanding of heteroepitaxy in radial heterostructures at nanoscale and building the three dimensional heterostructures for the various applications. In addition, the effect of the defect formation on nanomaterial’s functionality is investigated by electrochemical performance test. The Si/Ge core/shell nanowire heterostructures enhance the gravimetric capacity of lithium ion battery anodes under fast charging/discharging rates compared to Si nanowires. However, the induced structural defects hamper lithiation of the Si/Ge core/shell nanowire heterostructure.« less

Enhanced characterization of singly protonated phosphopeptide ions by femtosecond laser-induced ionization/dissociation tandem mass spectrometry (fs-LID-MS/MS).

PubMed

Smith, Scott A; Kalcic, Christine L; Safran, Kyle A; Stemmer, Paul M; Dantus, Marcos; Reid, Gavin E

2010-12-01

To develop an improved understanding of the regulatory role that post-translational modifications (PTMs) involving phosphorylation play in the maintenance of normal cellular function, tandem mass spectrometry (MS/MS) strategies coupled with ion activation techniques such as collision-induced dissociation (CID) and electron-transfer dissociation (ETD) are typically employed to identify the presence and site-specific locations of the phosphate moieties within a given phosphoprotein of interest. However, the ability of these techniques to obtain sufficient structural information for unambiguous phosphopeptide identification and characterization is highly dependent on the ion activation method employed and the properties of the precursor ion that is subjected to dissociation. Herein, we describe the application of a recently developed alternative ion activation technique for phosphopeptide analysis, termed femtosecond laser-induced ionization/dissociation (fs-LID). In contrast to CID and ETD, fs-LID is shown to be particularly suited to the analysis of singly protonated phosphopeptide ions, yielding a wide range of product ions including a, b, c, x, y, and z sequence ions, as well as ions that are potentially diagnostic of the positions of phosphorylation (e.g., 'a(n)+1-98'). Importantly, the lack of phosphate moiety losses or phosphate group 'scrambling' provides unambiguous information for sequence identification and phosphorylation site characterization. Therefore, fs-LID-MS/MS can serve as a complementary technique to established methodologies for phosphoproteomic analysis. Copyright © 2010. Published by Elsevier Inc.

Evaluation of Ion Mobility-Mass Spectrometry for Comparative Analysis of Monoclonal Antibodies

NASA Astrophysics Data System (ADS)

Ferguson, Carly N.; Gucinski-Ruth, Ashley C.

2016-05-01

Analytical techniques capable of detecting changes in structure are necessary to monitor the quality of monoclonal antibody drug products. Ion mobility mass spectrometry offers an advanced mode of characterization of protein higher order structure. In this work, we evaluated the reproducibility of ion mobility mass spectrometry measurements and mobiligrams, as well as the suitability of this approach to differentiate between and/or characterize different monoclonal antibody drug products. Four mobiligram-derived metrics were identified to be reproducible across a multi-day window of analysis. These metrics were further applied to comparative studies of monoclonal antibody drug products representing different IgG subclasses, manufacturers, and lots. These comparisons resulted in some differences, based on the four metrics derived from ion mobility mass spectrometry mobiligrams. The use of collision-induced unfolding resulted in more observed differences. Use of summed charge state datasets and the analysis of metrics beyond drift time allowed for a more comprehensive comparative study between different monoclonal antibody drug products. Ion mobility mass spectrometry enabled detection of differences between monoclonal antibodies with the same target protein but different production techniques, as well as products with different targets. These differences were not always detectable by traditional collision cross section studies. Ion mobility mass spectrometry, and the added separation capability of collision-induced unfolding, was highly reproducible and remains a promising technique for advanced analytical characterization of protein therapeutics.

Fragmentation study of iridoid glucosides through positive and negative electrospray ionization, collision-induced dissociation and tandem mass spectrometry.

PubMed

Es-Safi, Nour-Eddine; Kerhoas, Lucien; Ducrot, Paul-Henri

2007-01-01

Mass spectrometric methodology based on the combined use of positive and negative electrospray ionization, collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS) has been applied to the mass spectral study of a series of six naturally occurring iridoids through in-source fragmentation of the protonated [M+H]+, deprotonated [M--H]- and sodiated [M+Na]+ ions. This led to the unambiguous determination of the molecular masses of the studied compounds and allowed CID spectra of the molecular ions to be obtained. Valuable structural information regarding the nature of both the glycoside and the aglycone moiety was thus obtained. Glycosidic cleavage and ring cleavages of both aglycone and sugar moieties were the major fragmentation pathways observed during CID, where the losses of small molecules, the cinnamoyl and the cinnamate parts were also observed. The formation of the ionized aglycones, sugars and their product ions was thus obtained giving information on their basic skeleton. The protonated, i.e. [M+H]+ and deprotonated [M--H]-, ions were found to fragment mainly by glycosidic cleavages. MS/MS spectra of the [M+Na]+ ions gave complementary information for the structural characterization of the studied compounds. Unlike the dissociation of protonated molecular ions, that of sodiated molecules also provided sodiated sugar fragments where the C0+ fragment corresponding to the glucose ion was obtained as base peak for all the studied compounds. Copyright (c) 2007 John Wiley & Sons, Ltd.

Structural mechanism of ligand activation in human calcium-sensing receptor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geng, Yong; Mosyak, Lidia; Kurinov, Igor

2016-07-19

Human calcium-sensing receptor (CaSR) is a G-protein-coupled receptor (GPCR) that maintains extracellular Ca 2+homeostasis through the regulation of parathyroid hormone secretion. It functions as a disulfide-tethered homodimer composed of three main domains, the Venus Flytrap module, cysteine-rich domain, and seven-helix transmembrane region. Here, we present the crystal structures of the entire extracellular domain of CaSR in the resting and active conformations. We provide direct evidence that L-amino acids are agonists of the receptor. In the active structure, L-Trp occupies the orthosteric agonist-binding site at the interdomain cleft and is primarily responsible for inducing extracellular domain closure to initiate receptor activation.more » Our structures reveal multiple binding sites for Ca 2+and PO 4 3-ions. Both ions are crucial for structural integrity of the receptor. While Ca 2+ions stabilize the active state, PO 4 3-ions reinforce the inactive conformation. The activation mechanism of CaSR involves the formation of a novel dimer interface between subunits.« less

Coulomb spin liquid in anion-disordered pyrochlore Tb 2Hf 2O 7

DOE PAGES

Sibille, Romain; Lhotel, Elsa; Hatnean, Monica Ciomaga; ...

2017-10-12

Here, the charge ordered structure of ions and vacancies characterizing rare-earth pyrochlore oxides serves as a model for the study of geometrically frustrated magnetism. The organization of magnetic ions into networks of corner-sharing tetrahedra gives rise to highly correlated magnetic phases with strong fluctuations, including spin liquids and spin ices. It is an open question how these ground states governed by local rules are affected by disorder. Here we demonstrate in the pyrochlore Tb 2Hf 2O 7, that the vicinity of the disordering transition towards a defective fluorite structure translates into a tunable density of anion Frenkel disorder while cationsmore » remain ordered. Quenched random crystal fields and disordered exchange interactions can therefore be introduced into otherwise perfect pyrochlore lattices of magnetic ions. We show that disorder can play a crucial role in preventing long-range magnetic order at low temperatures, and instead induces a strongly fluctuating Coulomb spin liquid with defect-induced frozen magnetic degrees of freedom.« less

Ion-bombardment of nickel (110) at elevated temperature

NASA Astrophysics Data System (ADS)

Peddinti, Vijay Kumar

The goal of this thesis is to study the behavior of ion-induced defects at the Y point on the Ni (110) surface at elevated temperatures. The electronic structure of the surface is examined using inverse photoemission spectroscopy (IPES), and the geometric structure is observed using low energy electron diffraction (LEED). These measurements lead to a better understanding of the surface properties. The clean Ni (110) surface exhibits a peak ˜ 2.6 eV above the Fermi level, indicating an unoccupied surface state near the Y point of the surface Brillouin zone (SBZ). Defects are induced by low energy ion bombardment at various temperatures, which result in a decrease of the peak intensity. The surface state eventually disappears when bombarded for longer times. We also observed that the surface heals faster when the crystal is being simultaneously sputtered and annealed at higher versus lower temperature. Finally the data for annealing while sputtering versus annealing after sputtering does not seem to exhibit much difference.

Effect of gallium environment on infrared emission in Er3+-doped gallium– antimony– sulfur glasses

PubMed Central

Jiao, Qing; Li, Ge; Li, Lini; Lin, Changgui; Wang, Guoxiang; Liu, Zijun; Dai, Shixun; Xu, Tiefeng; Zhang, Qinyuan

2017-01-01

Gallium-based Ga–Sb–S sulfide glasses was elaborated and studied. A relationship between the structure, composition, and optical properties of the glass has been established. The effects of the introduction of Ga on the structure using infrared and Raman spectroscopies and on the Er3+-doped IR emission have been discussed. The results show that incorporation of Ga induced the dissociation of [SbS3] pyramids units and the formation of tetrahedral [GaS4] units. The dissolved rare earth ions are separated around the Ga–S bonding and the infrared emission quenching are controlled. Moreover, continuous introduction of Er ions into the glass forms more Er–S bonds through the further aggregation surrounding the [GaS4] units. In return, the infrared emission intensity decreased with excessive Er ion addition. This phenomenon is correlated with the recurrence concentration quenching effect induced by the increase of [GaS4] units. PMID:28106143

Ionization-induced annealing of pre-existing defects in silicon carbide

DOE PAGES

Zhang, Yanwen; Sachan, Ritesh; Pakarinen, Olli H.; ...

2015-08-12

A long-standing objective in materials research is to find innovative ways to remove preexisting damage and heal fabrication defects or environmentally induced defects in materials. Silicon carbide (SiC) is a fascinating wide-band gap semiconductor for high-temperature, high-power, high-frequency applications. Its high corrosion and radiation resistance makes it a key refractory/structural material with great potential for extremely harsh radiation environments. Here we show that the energy transferred to the electron system of SiC by energetic ions via inelastic ionization processes results in a highly localized thermal spike that can effectively heal preexisting defects and restore the structural order. This work revealsmore » an innovative self-healing process using highly ionizing ions, and it describes a critical aspect to be considered in modeling SiC performance as either a functional or a structural material for device applications or high-radiation environments.« less

Helical Structure Determines Different Susceptibilities of dsDNA, dsRNA, and tsDNA to Counterion-Induced Condensation

PubMed Central

Kornyshev, Alexei A.; Leikin, Sergey

2013-01-01

Recent studies of counterion-induced condensation of nucleic acid helices into aggregates produced several puzzling observations. For instance, trivalent cobalt hexamine ions condensed double-stranded (ds) DNA oligomers but not their more highly charged dsRNA counterparts. Divalent alkaline earth metal ions condensed triple-stranded (ts) DNA oligomers but not dsDNA. Here we show that these counterintuitive experimental results can be rationalized within the electrostatic zipper model of interactions between molecules with helical charge motifs. We report statistical mechanical calculations that reveal dramatic and nontrivial interplay between the effects of helical structure and thermal fluctuations on electrostatic interaction between oligomeric nucleic acids. Combining predictions for oligomeric and much longer helices, we also interpret recent experimental studies of the role of counterion charge, structure, and chemistry. We argue that an electrostatic zipper attraction might be a major or even dominant force in nucleic acid condensation. PMID:23663846

Enantiomer-Selective Photo-Induced Reaction of Protonated Tryptophan with Disaccharides in the Gas Phase

NASA Astrophysics Data System (ADS)

Doan, Thuc N.; Fujihara, Akimasa

2018-03-01

In order to investigate chemical evolution in interstellar molecular clouds, enantiomer-selective photo-induced chemical reactions between an amino acid and disaccharides in the gas phase were examined using a tandem mass spectrometer containing an electrospray ionization source and a cold ion trap. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of protonated tryptophan (Trp) enantiomers with disaccharides consisting of two d-glucose units, such as d-maltose or d-cellobiose, were obtained by photoexcitation of the indole ring of Trp. NH2CHCOOH loss via cleavage of the Cα-Cβ bond in Trp induced by hydrogen atom transfer from the NH3 + group of a protonated Trp was observed in a noncovalent heterochiral H+( l-Trp)( d-maltose) complex. In contrast, a photo-induced chemical reaction forming the product ion with m/z 282 occurs in homochiral H+( d-Trp)( d-maltose). For d-cellobiose, both NH2CHCOOH elimination and the m/z 282 product ion were observed, and no enantiomer-selective phenomena occurred. The m/z 282 product ion indicates that the photo-induced C-glycosylation, which links d-glucose residues to the indole moiety of Trp via a C-C bond, can occur in cold gas-phase noncovalent complexes, and its enantiomer-selectivity depends on the structure of the disaccharide.

UV-visible, Raman and E.S.R. studies of gamma-irradiated NiO-doped sodium metaphosphate glasses.

PubMed

ElBatal, Fatma H; Morsi, Reham M; Ouis, Mona A; Marzouk, Samir Y

2010-11-01

UV-visible spectroscopic measurements of Ni-doped sodium phosphate glasses were carried out before and after successive gamma irradiation. The undoped glass reveals strong UV absorption originating from trace iron impurities. NiO-doped glasses show characteristic absorption bands due mainly to octahedral coordination of Ni(2+) ions. Gamma irradiation produces induced bands generated from intrinsic defects and extrinsic defects. The changes in the spectroscopic data are discussed in relation to the structural evolution caused by the changes in composition and coordination state of nickel ions. The change in the growth behaviour of the induced bands is related to the annihilation or approach saturation of these characteristic induced bands. Raman and E.S.R. spectroscopic measurements confirm the presence of nickel as Ni(2+) ions in octahedral state. Copyright © 2010 Elsevier B.V. All rights reserved.

Structural identification of triacylglycerol isomers using electron impact excitation of ions from organics (EIEIO).

PubMed

Baba, Takashi; Campbell, J Larry; Le Blanc, J C Yves; Baker, Paul R S

2016-11-01

Electron-induced dissociation or electron impact excitation of ions from organics (EIEIO) was applied to triacylglycerols (TAGs) for in-depth molecular structure analysis using MS. In EIEIO, energetic electrons (∼10 eV) fragmented TAG ions to allow for regioisomeric assignment of identified acyl groups at the sn-2 or sn-1/3 positions of the glycerol backbone. In addition, carbon-carbon double bond locations within the acyl chains could also be assigned by EIEIO. Beyond the analysis of lipid standards, this technique was applied to edible oils and natural lipid extracts to demonstrate the power of this method to provide in-depth structural elucidation of TAG molecular species. Copyright © 2016 by the American Society for Biochemistry and Molecular Biology, Inc.

Tracking the Chemical Transformations at the Brønsted Acid Site upon Water-Induced Deprotonation in a Zeolite Pore

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vjunov, Aleksei; Wang, Meng; Govind, Niranjan

We report the structural changes induced by Brønsted acidic site deprotonation in a zeolite with MFI structure as a function of temperature up to 430°C using in situ Al K-edge X-ray absorption fine structure spectroscopy (XAFS). At ambient conditions, the protons are present as hydrated hydronium ions (H3O+(H2O)n) that are ion-paired to the anionic, Al tetrahedral (T) site. At elevated temperatures, loss of water molecules hydrating the hydronium ions leads to an unstable free hydronium ion that disso-ciates to form the hydroxylated T-site. The formation of this (-O3)-Al-(OH-) species leads to the elongation of one of the four Al-O bondsmore » and causes significant distortion of the tetrahedral symmetry about the Al atom. This distortion leads to the appearance of new pre-edge features in the Al K-edge X-ray absorption near edge structure (XANES) spectra. The pre-edge peak assignment is confirmed by time-dependent density functional theory calculation of the XANES spectrum. The XANES spectra are also sensitive to solutes or solvent that are in proximity to the T-site. A second structural transition occurs at about the same temperature, namely the conversion of a minor fraction of extra-framework octahedral Al present in the sample at ambient conditions to a tetrahedral species through the de-coordination of H2O-ligands. Both IR spectroscopy and thermogravimetric analysis (TGA) are further used to confirm the overall chemical transformation of the T-site.« less

Entropy-Driven Folding of an RNA Helical Junction: An Isothermal Titration Calorimetric Analysis of the Hammerhead Ribozyme†

PubMed Central

Mikulecky, Peter J.; Takach, Jennifer C.; Feig, Andrew L.

2008-01-01

Helical junctions are extremely common motifs in naturally occurring RNAs, but little is known about the thermodynamics that drive their folding. Studies of junction folding face several challenges: non-two-state folding behavior, superposition of secondary and tertiary structural energetics, and drastically opposing enthalpic and entropic contributions to folding. Here we describe a thermodynamic dissection of the folding of the hammerhead ribozyme, a three-way RNA helical junction, by using isothermal titration calorimetry of bimolecular RNA constructs. By using this method, we show that tertiary folding of the hammerhead core occurs with a highly unfavorable enthalpy change, and is therefore entropically driven. Furthermore, the enthalpies and heat capacities of core folding are the same whether supported by monovalent or divalent ions. These properties appear to be general to the core sequence of bimolecular hammerhead constructs. We present a model for the ion-induced folding of the hammerhead core that is similar to those advanced for the folding of much larger RNAs, involving ion-induced collapse to a structured, non-native state accompanied by rearrangement of core residues to produce the native fold. In agreement with previous enzymological and structural studies, our thermodynamic data suggest that the hammerhead structure is stabilized in vitro predominantly by diffusely bound ions. Our approach addresses several significant challenges that accompany the study of junction folding, and should prove useful in defining the thermodynamic determinants of stability in these important RNA motifs. PMID:15134461

Bio-inspired metal ions regulate the structure evolution of self-assembled peptide-based nanoparticles

NASA Astrophysics Data System (ADS)

Xu, An-Ping; Yang, Pei-Pei; Yang, Chao; Gao, Yu-Juan; Zhao, Xiao-Xiao; Luo, Qiang; Li, Xiang-Dan; Li, Li-Zhong; Wang, Lei; Wang, Hao

2016-07-01

We report an assembly and transformation process of a supramolecular module, BP-KLVFF-RGD (BKR) in solution and on specific living cell surfaces for imaging and treatment. The BKR self-assembled into nanoparticles, which further transformed into nanofibers in situ induced by coordination with Ca2+ ions.We report an assembly and transformation process of a supramolecular module, BP-KLVFF-RGD (BKR) in solution and on specific living cell surfaces for imaging and treatment. The BKR self-assembled into nanoparticles, which further transformed into nanofibers in situ induced by coordination with Ca2+ ions. Electronic supplementary information (ESI) available: Experimental details; Fig. S1-S9. See DOI: 10.1039/c6nr03580a

Unified first principles description from warm dense matter to ideal ionized gas plasma: electron-ion collisions induced friction.

PubMed

Dai, Jiayu; Hou, Yong; Yuan, Jianmin

2010-06-18

Electron-ion interactions are central to numerous phenomena in the warm dense matter (WDM) regime and at higher temperature. The electron-ion collisions induced friction at high temperature is introduced in the procedure of ab initio molecular dynamics using the Langevin equation based on density functional theory. In this framework, as a test for Fe and H up to 1000 eV, the equation of state and the transition of electronic structures of the materials with very wide density and temperature can be described, which covers a full range of WDM up to high energy density physics. A unified first principles description from condensed matter to ideal ionized gas plasma is constructed.

Self-consistent Model of Magnetospheric Ring Current and Propagating Electromagnetic Ion Cyclotron Waves. 2. Wave Induced Ring Current Precipitation and Thermal Electron Heating

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Gamayunov, K. V.; Gallagher, D. L.; Kozyra, J. U.; Liemohn, M. W.

2007-01-01

This paper continues presentation and discussion of the results from our new global self-consistent theoretical model of interacting ring current ions and propagating electromagnetic ion cyclotron waves [Khazanov et al., 2006]. To study the effects of electromagnetic ion cyclotron wave propagation and refraction on the wave induced ring current precipitation and heating of the thermal plasmaspheric electrons, we simulate the May 1998 storm. The main findings after a simulation can be summarized as follows. Firstly, the wave induced ring current precipitation exhibits quite a lot of fine structure, and is highly organized by location of the plasmapause gradient. The strongest fluxes of about 4 x 10(exp 6) (cm(raised dot) s(raised dot) sr(raised dot) (sup -1)) are observed during the maill and early recovery phases of the storm. The very interesting and probably more important finding is that in a number of cases the most intense precipitating fluxes are not connected to the most intense waves in simple manner. The characteristics of the wave power spectral density distribution over the wave normal angle are extremely crucial for the effectiveness of the ring current ion scattering. Secondly, comparison of the global proton precipitating patterns with the results from RAM [Kozyra et al., 1997a] reveals that although we observe a qualitative agreement between the localizations of the wave induced precipitations in the models, there is no quantitative agreement between the magnitudes of the fluxes. The quantitative differences are mainly due to a qualitative difference between the characteristics of the wave power spectral density distributions over the wave normal angle in RAM and in our model. Thirdly, the heat fluxes to plasmaspheric electrons caused by Landau resonate energy absorption from electromagnetic ion cyclotron waves are observed in the postnoon-premidnight MLT sector, and can reach the magnitude of 10(exp 11) eV/(cm(sup 2)(raised dot)s). The Coulomb energy degradation of the RC H(+) and O(+) ions maximizes at about 10(exp 11) (eV/(cm(sup 2) (raised dot) s), and typically leads to electron energy deposition rates of about 2(raised dot) 10(exp 10) (eV/(cm(sup 2)(raised dot)s) which are observed during two periods; 32-48 hours, and 76-86 hours after 1 May, 0000 UT. The theoretically derived spatial structure of the thermal electron heating caused by interaction of the ring current with the plasmasphere is strongly supported by concurrent and conjugate plasma measurements from the plasmasphere, ring current, and topside ionosphere [Gurgiolo et al., 2005]. Finally, the wave induced intense electron heating has a structure of the spot-like patches along the most enhanced density gradients in the plasmasphere boundary layer and can be a possible driver to the observed but still not explained small-scale structures of enhanced emissions in the stable auroral red arcs.

Implementation of dipolar direct current (DDC) collision-induced dissociation in storage and transmission modes on a quadrupole/time-of-flight tandem mass spectrometer.

PubMed

Webb, Ian K; Londry, Frank A; McLuckey, Scott A

2011-09-15

Means for effecting dipolar direct current collision-induced dissociation (DDC CID) on a quadrupole/time-of-flight in a mass spectrometer have been implemented for the broadband dissociation of a wide range of analyte ions. The DDC fragmentation method in electrodynamic storage and transmission devices provides a means for inducing fragmentation of ions over a large mass-to-charge range simultaneously. It can be effected within an ion storage step in a quadrupole collision cell that is operated as a linear ion trap or as ions are continuously transmitted through the collision cell. A DDC potential is applied across one pair of rods in the quadrupole collision cell of a QqTOF hybrid mass spectrometer to effect fragmentation. In this study, ions derived from a small drug molecule, a model peptide, a small protein, and an oligonucleotide were subjected to the DDC CID method in either an ion trapping or an ion transmission mode (or both). Several key experimental parameters that affect DDC CID results, such as time, voltage, low mass cutoff, and bath gas pressure, are illustrated with protonated leucine enkephalin. The DDC CID dissociation method gives a readily tunable, broadband tool for probing the primary structures of a wide range of analyte ions. The method provides an alternative to the narrow resonance conditions of conventional ion trap CID and it can access more extensive sequential fragmentation, depending upon conditions. The DDC CID approach constitutes a collision analog to infrared multiphoton dissociation (IRMPD). Copyright © 2011 John Wiley & Sons, Ltd.

Swift heavy ion irradiation studies of GdFeO3 orthoferrite thin films

NASA Astrophysics Data System (ADS)

Kaur, Pawanpreet; Pandit, Rabia; Sharma, K. K.; Kumar, Ravi

2018-04-01

Thin films of GdFeO3, orthoferrite have been grown on MgO (001) substrate by pulsed laser deposition technique (PLD) to investigate the effect of swift heavy ion irradiation on their structural and magnetic properties. Thin films were irradiated with 200 MeV Ag15+ ions with fluence of 1×1011ions/cm2. The results of X-ray diffraction, atomic force microscopy and vibrating sample magnetometer characterization techniques are found to be different for the irradiated film from that of the pristine sample. The modifications in the irradiated samples are explained in terms of the ion-induced disorder.

A novel colorimetric fluoride sensor based on a semi-rigid chromophore controlled by hydrogen bonding.

PubMed

Li, Jiling; Xu, Xiaoyong; Shao, Xusheng; Li, Zhong

2015-12-01

A novel semi-rigid latent chromophore E1, containing an amide subunit activated by an adjacent semi-rigid intramolecular hydrogen-bonding (IHB) unit, was designed for the detection of fluoride ion by the 'naked-eye' in CH3CN. Comparative studies on structural analogs (E2, E3, and E4) provided significant insight into the structural and functional role of the amide N-H and IHB segment in the selective recognition of fluoride ions. The deprotonation of the amide N-H followed by the enhancement of intramolecular charge transfer (ICT) induced the colorimetric detection of E1 for fluoride ion. Copyright © 2015 John Wiley & Sons, Ltd.

Characterization of ion-irradiation-induced nanodot structures on InP surfaces by atom probe tomography.

PubMed

Gnaser, Hubert; Radny, Tobias

2015-12-01

Surfaces of InP were bombarded by 1.9 keV Ar(+) ions under normal incidence. The total accumulated ion fluence the samples were exposed to was varied from 1 × 10(17) cm(-2) to 3 × 10(18)cm(-2) and ion flux densities f of (0.4-2) × 10(14) cm(-2) s(-1) were used. Nanodot structures were found to evolve on the surface from these ion irradiations, their dimensions however, depend on the specific bombardment conditions. The resulting surface morphology was examined by atomic force microscopy (AFM). As a function of ion fluence, the mean radius, height, and spacing of the dots can be fitted by power-law dependences. In order to determine possible local compositional changes in these nanostructures induced by ion impact, selected samples were prepared for atom probe tomography (APT). The results indicate that by APT the composition of individual InP nanodots evolving under ion bombardment could be examined with atomic spatial resolution. At the InP surface, the values of the In/P concentration ratio are distinctly higher over a distance of ~1 nm and amount to 1.3-1.8. However, several aspects critical for the analyses were identified: (i) because of the small dimensions of these nanostructures a successful tip preparation proved very challenging. (ii) The elemental compositions obtained from APT were found to be influenced pronouncedly by the laser pulse energy; typically, low energies result in the correct stoichiometry whereas high ones lead to an inhomogeneous evaporation from the tips and deviations from the nominal composition. (iii) Depending again on the laser energy, a prolific emission of Pn cluster ions was observed, with n ≤ 11. Copyright © 2015. Published by Elsevier B.V.

Raman microspectroscopic study of effects of Na(I) and Mg(II) ions on low pH induced DNA structural changes.

PubMed

Muntean, C M; Segers-Nolten, G M J

2003-01-01

In this work a confocal Raman microspectrometer is used to investigate the influence of Na(+) and Mg(2+) ions on the DNA structural changes induced by low pH. Measurements are carried out on calf thymus DNA at neutral pH (7) and pH 3 in the presence of low and high concentrations of Na(+) and Mg(2+) ions, respectively. It is found that low concentrations of Na(+) ions do not protect DNA against binding of H(+). High concentrations of monovalent ions can prevent protonation of the DNA double helix. Our Raman spectra show that low concentrations of Mg(2+) ions partly protect DNA against protonation of cytosine (line at 1262 cm(-1)) but do not protect adenine and guanine N(7) against binding of H(+) (characteristic lines at 1304 and 1488 cm(-1), respectively). High concentrations of Mg(2+) can prevent protonation of cytosine and protonation of adenine (disruption of AT pairs). By analyzing the line at 1488 cm(-1), which obtains most of its intensity from a guanine vibration, high magnesium salt protect the N(7) of guanine against protonation. A high salt concentration can prevent protonation of guanine, cytosine, and adenine in DNA. Higher salt concentrations cause less DNA protonation than lower salt concentrations. Magnesium ions are found to be more effective in protecting DNA against binding of H(+) as compared with calcium ions presented in a previous study. Divalent metal cations (Mg(2+), Ca(2+)) are more effective in protecting DNA against protonation than monovalent ions (Na(+)). Copyright 2003 Wiley Periodicals, Inc. Biopolymers (Biospectroscopy) 72: 000-000, 2003

Permanent bending and alignment of ZnO nanowires.

PubMed

Borschel, Christian; Spindler, Susann; Lerose, Damiana; Bochmann, Arne; Christiansen, Silke H; Nietzsche, Sandor; Oertel, Michael; Ronning, Carsten

2011-05-06

Ion beams can be used to permanently bend and re-align nanowires after growth. We have irradiated ZnO nanowires with energetic ions, achieving bending and alignment in different directions. Not only the bending of single nanowires is studied in detail, but also the simultaneous alignment of large ensembles of ZnO nanowires. Computer simulations reveal how the bending is initiated by ion beam induced damage. Detailed structural characterization identifies dislocations to relax stresses and make the bending and alignment permanent, even surviving annealing procedures.

Inducing superconductivity in Weyl semimetal microstructures by selective ion sputtering.

PubMed

Bachmann, Maja D; Nair, Nityan; Flicker, Felix; Ilan, Roni; Meng, Tobias; Ghimire, Nirmal J; Bauer, Eric D; Ronning, Filip; Analytis, James G; Moll, Philip J W

2017-05-01

By introducing a superconducting gap in Weyl or Dirac semimetals, the superconducting state inherits the nontrivial topology of their electronic structure. As a result, Weyl superconductors are expected to host exotic phenomena, such as nonzero-momentum pairing due to their chiral node structure, or zero-energy Majorana modes at the surface. These are of fundamental interest to improve our understanding of correlated topological systems, and, moreover, practical applications in phase-coherent devices and quantum applications have been proposed. Proximity-induced superconductivity promises to allow these experiments on nonsuperconducting Weyl semimetals. We show a new route to reliably fabricate superconducting microstructures from the nonsuperconducting Weyl semimetal NbAs under ion irradiation. The significant difference in the surface binding energy of Nb and As leads to a natural enrichment of Nb at the surface during ion milling, forming a superconducting surface layer ( T c ~ 3.5 K). Being formed from the target crystal itself, the ideal contact between the superconductor and the bulk may enable an effective gapping of the Weyl nodes in the bulk because of the proximity effect. Simple ion irradiation may thus serve as a powerful tool for the fabrication of topological quantum devices from monoarsenides, even on an industrial scale.

Inducing superconductivity in Weyl semimetal microstructures by selective ion sputtering

PubMed Central

Bachmann, Maja D.; Nair, Nityan; Flicker, Felix; Ilan, Roni; Meng, Tobias; Ghimire, Nirmal J.; Bauer, Eric D.; Ronning, Filip; Analytis, James G.; Moll, Philip J. W.

2017-01-01

By introducing a superconducting gap in Weyl or Dirac semimetals, the superconducting state inherits the nontrivial topology of their electronic structure. As a result, Weyl superconductors are expected to host exotic phenomena, such as nonzero-momentum pairing due to their chiral node structure, or zero-energy Majorana modes at the surface. These are of fundamental interest to improve our understanding of correlated topological systems, and, moreover, practical applications in phase-coherent devices and quantum applications have been proposed. Proximity-induced superconductivity promises to allow these experiments on nonsuperconducting Weyl semimetals. We show a new route to reliably fabricate superconducting microstructures from the nonsuperconducting Weyl semimetal NbAs under ion irradiation. The significant difference in the surface binding energy of Nb and As leads to a natural enrichment of Nb at the surface during ion milling, forming a superconducting surface layer (Tc ~ 3.5 K). Being formed from the target crystal itself, the ideal contact between the superconductor and the bulk may enable an effective gapping of the Weyl nodes in the bulk because of the proximity effect. Simple ion irradiation may thus serve as a powerful tool for the fabrication of topological quantum devices from monoarsenides, even on an industrial scale. PMID:28560340

GaN light-emitting device based on ionic liquid electrolyte

NASA Astrophysics Data System (ADS)

Hirai, Tomoaki; Sakanoue, Tomo; Takenobu, Taishi

2018-06-01

Ionic liquids (ILs) are attractive materials for fabricating unique hybrid devices based on electronics and electrochemistry; thus, IL-gated transistors and organic light-emitting devices of light-emitting electrochemical cells (LECs) are investigated for future low-voltage and high-performance devices. In LECs, voltage application induces the formation of electrochemically doped p–n homojunctions owing to ion rearrangements in composites of semiconductors and electrolytes, and achieves electron–hole recombination for light emission at the homojunctions. In this work, we applied this concept of IL-induced electrochemical doping to the fabrication of GaN-based light-emitting devices. We found that voltage application to the layered IL/GaN structure accumulated electrons on the GaN surface owing to ion rearrangements and improved the conductivity of GaN. The ion rearrangement also enabled holes to be injected by the strong electric field of electric double layers on hole injection contacts. This simultaneous injection of holes and electrons into GaN mediated by ions achieves light emission at a low voltage of around 3.4 V. The light emission from the simple IL/GaN structure indicates the usefulness of an electrochemical technique in generating light emission with great ease of fabrication.

Unraveling halide hydration: A high dilution approach.

PubMed

Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

2014-07-28

The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

NASA Astrophysics Data System (ADS)

Maleki, Hossein; Karanji, Ahmad K.; Majuta, Sandra; Maurer, Megan M.; Valentine, Stephen J.

2018-02-01

Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate ( in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.

Swift heavy ion induced modifications in optical and electrical properties of cadmium selenide thin films

NASA Astrophysics Data System (ADS)

Choudhary, Ritika; Chauhan, Rishi Pal

2017-07-01

The modification in various properties of thin films using high energetic ion beam is an exciting area of basic and applied research in semiconductors. In the present investigations, cadmium selenide (CdSe) thin films were deposited on ITO substrate using electrodeposition technique. To study the swift heavy ion (SHI) induced effects, the deposited thin films were irradiated with 120 MeV heavy Ag9+ ions using pelletron accelerator facility at IUAC, New Delhi, India. Structural phase transformation in CdSe thin film from metastable cubic phase to stable hexagonal phase was observed after irradiation leading to decrease in the band gap from 2.47 eV to 2.12 eV. The phase transformation was analyzed through X-ray diffraction patterns. During SHI irradiation, Generation of high temperature and pressure by thermal spike along the trajectory of incident ions in the thin films might be responsible for modification in the properties of thin films.[Figure not available: see fulltext.

Irradiation effects on multilayered W/ZrO2 film under 4 MeV Au ions

NASA Astrophysics Data System (ADS)

Wang, Hongwei; Gao, Yuan; Fu, Engang; Yang, Tengfei; Xue, Jianming; Yan, Sha; Chu, Paul K.; Wang, Yugang

2014-12-01

Irradiation induced structural changes in multilayered W/ZrO2 nanocomposites with periodic bilayer thicknesses of (7/14 nm) and (70/140 nm) were investigated following Au+ ion irradiation. The samples were irradiated by 4 MeV Au ions with fluences ranging from 6 × 1014 to 1 × 1016 ions/cm2. The immiscible W/ZrO2 interfaces remained unchanged without intermixing of the layers upon the irradiation. No voids were observed in the samples with different periodic layer thicknesses. The XRD and XTEM studies reveal thickness dependent microstructural changes in the samples. W and ZrO2 grains in the thinner (7/14 nm) bilayer sample exhibit significant resistance to grain growth compared to the thicker (70/140 nm) bilayer sample as well as a W monolayer film. The high fraction of flat interfaces as well as grain boundaries in multilayer films plays a role in suppressing ion irradiation-induced grain growth and void formation.

The LILIA (laser induced light ions acceleration) experiment at LNF

NASA Astrophysics Data System (ADS)

Agosteo, S.; Anania, M. P.; Caresana, M.; Cirrone, G. A. P.; De Martinis, C.; Delle Side, D.; Fazzi, A.; Gatti, G.; Giove, D.; Giulietti, D.; Gizzi, L. A.; Labate, L.; Londrillo, P.; Maggiore, M.; Nassisi, V.; Sinigardi, S.; Tramontana, A.; Schillaci, F.; Scuderi, V.; Turchetti, G.; Varoli, V.; Velardi, L.

2014-07-01

Laser-matter interaction at relativistic intensities opens up new research fields in the particle acceleration and related secondary sources, with immediate applications in medical diagnostics, biophysics, material science, inertial confinement fusion, up to laboratory astrophysics. In particular laser-driven ion acceleration is very promising for hadron therapy once the ion energy will attain a few hundred MeV. The limited value of the energy up to now obtained for the accelerated ions is the drawback of such innovative technique to the real applications. LILIA (laser induced light ions acceleration) is an experiment now running at LNF (Frascati) with the goal of producing a real proton beam able to be driven for significant distances (50-75 cm) away from the interaction point and which will act as a source for further accelerating structure. In this paper the description of the experimental setup, the preliminary results of solid target irradiation and start to end simulation for a post-accelerated beam up to 60 MeV are given.

Processing method for forming dislocation-free SOI and other materials for semiconductor use

DOEpatents

Holland, Orin Wayne; Thomas, Darrell Keith; Zhou, Dashun

1997-01-01

A method for preparing a silicon-on-insulator material having a relatively defect-free Si overlayer involves the implanting of oxygen ions within a silicon body and the interruption of the oxygen-implanting step to implant Si ions within the silicon body. The implanting of the oxygen ions develops an oxide layer beneath the surface of the silicon body, and the Si ions introduced by the Si ion-implanting step relieves strain which is developed in the Si overlayer during the implanting step without the need for any intervening annealing step. By relieving the strain in this manner, the likelihood of the formation of strain-induced defects in the Si overlayer is reduced. In addition, the method can be carried out at lower processing temperatures than have heretofore been used with SIMOX processes of the prior art. The principles of the invention can also be used to relieve negative strain which has been induced in a silicon body of relatively ordered lattice structure.

Kinetic Monte Carlo simulations of ion-induced ripple formation: Dependence on flux, temperature, and defect concentration in the linear regime

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chason, E.; Chan, W. L.; Bharathi, M. S.

Low-energy ion bombardment produces spontaneous periodic structures (sputter ripples) on many surfaces. Continuum theories describe the pattern formation in terms of ion-surface interactions and surface relaxation kinetics, but many features of these models (such as defect concentration) are unknown or difficult to determine. In this work, we present results of kinetic Monte Carlo simulations that model surface evolution using discrete atomistic versions of the physical processes included in the continuum theories. From simulations over a range of parameters, we obtain the dependence of the ripple growth rate, wavelength, and velocity on the ion flux and temperature. The results are discussedmore » in terms of the thermally dependent concentration and diffusivity of ion-induced surface defects. We find that in the early stages of ripple formation the simulation results are surprisingly well described by the predictions of the continuum theory, in spite of simplifying approximations used in the continuum model.« less

Extrinsic pseudocapacitve Li-ion storage of SnS anode via lithiation-induced structural optimization on cycling

NASA Astrophysics Data System (ADS)

Lian, Qingwang; Zhou, Gang; Liu, Jiatu; Wu, Chen; Wei, Weifeng; Chen, Libao; Li, Chengchao

2017-10-01

Here, we report a new enhanced extrinsic pseudocapacitve Li-ion storage mechanism via lithiation-induced structural optimization strategy. The flower-like C@SnS and bulk SnS exhibit initial capacity decay and subsequent increase of capacity on cycling. After a long-term lithiation/delithiation process, flower-like C@SnS and bulk SnS exhibit improved rate performance and reversible capacity in comparison with those of initial state. Moreover, a high capacity of 530 mAh g-1 is still remained even after 1550 cycles at a high current density of 5.0 A g-1 for flower-like C@SnS after pre-lithiation of 350 cycles. According to the comprehensive analysis of structural evolution and electrochemical performance, it demonstrates that SnS electrodes experience crystal size reduction and further amorphization on cycling, which enhances the reversibility of conversion reaction for SnS, leading to increasing capacity. On the other hand, surface-dominated extrinsic pseudocapacitive contribution results in enhanced rate performance because electrodes expose a large fraction of Li+ sites on surface or near-surface region with structural optimization on cycling. This study reveals that extrinsic pseudocapacitance of SnS can be stimulated via lithiation-induced structural optimization, which gives rise to high-rate and long-lived performances.

Asymmetric Preorganization of Inverted Pair Residues in the Sodium-Calcium Exchanger

PubMed Central

Giladi, Moshe; Almagor, Lior; van Dijk, Liat; Hiller, Reuben; Man, Petr; Forest, Eric; Khananshvili, Daniel

2016-01-01

In analogy with many other proteins, Na+/Ca2+ exchangers (NCX) adapt an inverted twofold symmetry of repeated structural elements, while exhibiting a functional asymmetry by stabilizing an outward-facing conformation. Here, structure-based mutant analyses of the Methanococcus jannaschii Na+/Ca2+ exchanger (NCX_Mj) were performed in conjunction with HDX-MS (hydrogen/deuterium exchange mass spectrometry) to identify the structure-dynamic determinants of functional asymmetry. HDX-MS identified hallmark differences in backbone dynamics at ion-coordinating residues of apo-NCX_Mj, whereas Na+or Ca2+ binding to the respective sites induced relatively small, but specific, changes in backbone dynamics. Mutant analysis identified ion-coordinating residues affecting the catalytic capacity (kcat/Km), but not the stability of the outward-facing conformation. In contrast, distinct “noncatalytic” residues (adjacent to the ion-coordinating residues) control the stability of the outward-facing conformation, but not the catalytic capacity. The helix-breaking signature sequences (GTSLPE) on the α1 and α2 repeats (at the ion-binding core) differ in their folding/unfolding dynamics, while providing asymmetric contributions to transport activities. The present data strongly support the idea that asymmetric preorganization of the ligand-free ion-pocket predefines catalytic reorganization of ion-bound residues, where secondary interactions with adjacent residues couple the alternating access. These findings provide a structure-dynamic basis for ion-coupled alternating access in NCX and similar proteins. PMID:26876271

Transition from Irradiation-Induced Amorphization to Crystallization in Nanocrystalline Silicon Carbide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Weilin; Jiao, Liang; Wang, Haiyan

2011-12-01

Response to irradiation of nanocrystalline 3C-SiC is studied using 2 MeV Au+ ions near the critical temperature for amorphization and is compared to the behavior of its monocrystalline counterpart under the identical irradiation conditions. The irradiated samples have been characterized using in-situ ion channeling, ex-situ x-ray diffraction, and helium ion microscopy. Compared to monocrystalline 3C-SiC, a faster amorphization process in the nanocrystalline material (average grain size = 3.3 nm) is observed at 500 K. However, the nanograin grows with increasing ion fluence at 550 K and the grain size tends to saturate at high fluences. The striking contrast demonstrates amore » sharp transition from irradiation-induced interface-driven amorphization at 500 K to crystallization at 550 K. The results could show potential impacts of nanocrystalline SiC on nuclear fuel cladding and structural components of next-generation nuclear energy systems.« less

Impact of the track structure of heavy charged particles on cytogenetic damage in human blood lymphocytes

NASA Astrophysics Data System (ADS)

Lee, Ryonfa; Nasonova, Elena; Sommer, Sylwetster; Hartel, Carola; Durante, Marco; Ritter, Sylvia

In space, astronauts are unavoidably exposed to charged particles from protons to irons. For a better estimate of the health risks of astronauts, further knowledge on the biological effects of charged particles, in particular the induction of cytogenetic damage is required. One im-portant factor that determines the biological response is the track structure of particles, i.e. their microscopic dose deposition in cells. The aim of the present study was to assess the influence of track structure of heavy ions on the yield and the quality of cytogenetic damage in human peripheral blood lymphocytes representing normal tissue. Cells were irradiated with 9.5 MeV/u C-ions or 990 MeV/u Fe-ions which have a comparable LET (175 keV/µm and 155 keV/µm, respectively) but a different track radius (2.3 and 6200 µm, respectively). When aberrations were analyzed in first cycle metaphases collected at different post-irradiation times (48-84 h) following fluorescence plus Giemsa staining, an increase in the aberration yield with sampling time was observed for both radiation qualities reflecting a damage dependent cell cycle progression delay to mitosis. The pronounced differences in the aberration frequency per cell are attributable to the stochastic distribution of particle traversals per cell nucleus (radius: 2.8 µm). Following C-ion exposure we found a high fraction of non-aberrant cells in samples collected at 48 h which represent cells not directly hit by a particle and slightly damaged cells that successfully repaired the induced lesions. In addition, at higher C-ion fluences the aberra-tion yield saturated, suggesting that a fraction of lymphocytes receiving multiple particle hits is not able to reach mitosis. On the other hand, at 48 h after Fe-ion exposure the proportion of non-aberrant cells is lower than after C-ion irradiation clearly reflecting the track structure of high energy particles (i.e. more homogeneous dose deposition compared to low energy C-ions). Furthermore, the aberration yield increased linearly with Fe-ion fluence. When aberrations were analyzed in first cycle G2 -PCC cells to account for the prolonged G2 arrest of damaged cells, the same trend was detected. However, the increase in the aberration yield with time and the saturation effect were less pronounced compared to metaphase samples. Altogether, these data show that the aberration analysis with multiple samplings is necessary for a reliable estimate of cytogenetic damage induced by charged particles. In particular, when damage is measured at one early time-point the effectiveness of low energy particles will be considerably underestimated. When the aberration spectrum induced by low energy C-ions and high en-ergy Fe-ions was compared, we did not find a difference. Preliminary data obtained with the high resolution mFISH-technique confirm this observation. (Work supported by BMBF, Bonn, under contract 02S8497)

M-BAND Study of Radiation-Induced Chromosome Aberrations in Human Epithelial Cells: Radiation Quality and Dose Rate Effects

NASA Technical Reports Server (NTRS)

Hada, Megumi; Cucinotta, Francis; Wu, Honglu

2009-01-01

The advantage of the multicolor banding in situ hybridization (mBAND) technique is its ability to identify both inter- (translocation to unpainted chromosomes) and intra- (inversions and deletions within a single painted chromosome) chromosome aberrations simultaneously. To study the detailed rearrangement of low- and high-LET radiation induced chromosome aberrations in human epithelial cells (CH184B5F5/M10) in vitro, we performed a series of experiments with Cs-137 gamma rays of both low and high dose rates, neutrons of low dose rate and 600 MeV/u Fe ions of high dose rate, with chromosome 3 painted with multi-binding colors. We also compared the chromosome aberrations in both 2- and 3-dimensional cell cultures. Results of these experiments revealed the highest chromosome aberration frequencies after low dose rate neutron exposures. However, detailed analysis of the radiation induced inversions revealed that all three radiation types induced a low incidence of simple inversions. Most of the inversions in gamma-ray irradiated samples were accompanied by other types of intra-chromosomal aberrations but few inversions were accompanied by inter-chromosomal aberrations. In contrast, neutrons and Fe ions induced a significant fraction of inversions that involved complex rearrangements of both inter- and intrachromosomal exchanges. The location of the breaks involved in chromosome exchanges was analyzed along the painted chromosome. The breakpoint distribution was found to be randomly localized on chromosome 3 after neutron or Fe ion exposure, whereas non-random distribution with clustering breakpoints was observed after -ray exposure. Our comparison of chromosome aberration yields between 2- and 3-dimensional cell cultures indicated a significant difference for gamma exposures, but not for Fe ion exposures. These experimental results indicated that the track structure of the radiation and the cellular/chromosome structure can both affect radiation-induced chromosome aberrations.

Study on structural recovery of graphite irradiated with swift heavy ions at high temperature

NASA Astrophysics Data System (ADS)

Pellemoine, F.; Avilov, M.; Bender, M.; Ewing, R. C.; Fernandes, S.; Lang, M.; Li, W. X.; Mittig, W.; Schein, M.; Severin, D.; Tomut, M.; Trautmann, C.; Zhang, F. X.

2015-12-01

Thin graphite foils bombarded with an intense high-energy (8.6 MeV/u) gold beam reaching fluences up to 1 × 1015 ions/cm2 lead to swelling and electrical resistivity changes. As shown earlier, these effects are diminished with increasing irradiation temperature. The work reported here extends the investigation of beam induced changes of these samples by structural analysis using synchrotron X-ray diffraction and transmission electron microscope. A nearly complete recovery from swelling at irradiation temperatures above about 1500 °C is identified.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moutanabbir, O.; Scholz, R.; Senz, S.

We investigated the microstructural transformations during hydrogen ion-induced splitting of GaN thin layers. Cross-sectional transmission electron microscopy and positron annihilation spectroscopy data show that the implanted region is decorated with a high density of 1-2 nm bubbles resulting from vacancy clustering during implantation. These nanobubbles persist up to 450 deg. C. Ion channeling data show a strong dechanneling enhancement in this temperature range tentatively attributed to strain-induced lattice distortion. The dechanneling level decreases following the formation of plateletlike structures at 475 deg. C. Extended internal surfaces develop around 550 deg. C leading to the exfoliation of GaN thin layer.

Effects of compositional complexity on the ion-irradiation induced swelling and hardening in Ni-containing equiatomic alloys

DOE PAGES

Jin, K.; Lu, C.; Wang, L. M.; ...

2016-04-14

The impact of compositional complexity on the ion-irradiation induced swelling and hardening is studied in Ni and six Ni-containing equiatomic alloys with face-centered cubic structure. The irradiation resistance at the temperature of 500 °C is improved by controlling the number and, especially, the type of alloying elements. Alloying with Fe and Mn has a stronger influence on swelling reduction than does alloying with Co and Cr. Lastly, the quinary alloy NiCoFeCrMn, with known excellent mechanical properties, has shown 40 times higher swelling tolerance than nickel.

Ion propulsion

NASA Technical Reports Server (NTRS)

Meserole, J. S.; Keefer, Dennis; Ruyten, Wilhelmus; Peng, Xiaohang

1995-01-01

An ion engine is a plasma thruster which produces thrust by extracting ions from the plasma and accelerating them to high velocity with an electrostatic field. The ions are then neutralized and leave the engine as high velocity neutral particles. The advantages of ion engines are high specific impulse and efficiency and their ability to operate over a wide range of input powers. In comparison with other electric thrusters, the ion engine has higher efficiency and specific impulse than thermal electric devices such as the arcjet, microwave, radiofrequency and laser heated thrusters and can operate at much lower current levels than the MPD thruster. However, the thrust level for an ion engine may be lower than a thermal electric thruster of the same operating power, consistent with its higher specific impulse, and therefore ion engines are best suited for missions which can tolerate longer duration propulsive phases. The critical issue for the ion engine is lifetime, since the prospective missions may require operation for several thousands of hours. The critical components of the ion engine, with respect to engine lifetime, are the screen and accelerating grid structures. Typically, these are large metal screens that must support a large voltage difference and maintain a small gap between them. Metallic whisker growth, distortion and vibration can lead to arcing, and over a long period of time ion sputtering will erode the grid structures and change their geometry. In order to study the effects of long time operation of the grid structure, we are developing computer codes based on the Particle-In-Cell (PIC) technique and Laser Induced Fluorescence (LIF) diagnostic techniques to study the physical processes which control the performance and lifetime of the grid structures.

Electron Transfer Ion/Ion Reactions in a Three-Dimensional Quadrupole Ion Trap: Reactions of Doubly and Triply Protonated Peptides with SO2·−

PubMed Central

Pitteri, Sharon J.; Chrisman, Paul A.; Hogan, Jason M.; McLuckey, Scott A.

2005-01-01

Ion–ion reactions between a variety of peptide cations (doubly and triply charged) and SO2 anions have been studied in a 3-D quadrupole ion trap, resulting in proton and electron transfer. Electron transfer dissociation (ETD) gives many c- and z-type fragments, resulting in extensive sequence coverage in the case of triply protonated peptides with SO2·−. For triply charged neurotensin, in which a direct comparison can be made between 3-D and linear ion trap results, abundances of ETD fragments relative to one another appear to be similar. Reactions of doubly protonated peptides with SO2·− give much less structural information from ETD than triply protonated peptides. Collision-induced dissociation (CID) of singly charged ions formed in reactions with SO2·− shows a combination of proton and electron transfer products. CID of the singly charged species gives more structural information than ETD of the doubly protonated peptide, but not as much information as ETD of the triply protonated peptide. PMID:15762593

Quercetagetin-Loaded Zein-Propylene Glycol Alginate Ternary Composite Particles Induced by Calcium Ions: Structure Characterization and Formation Mechanism.

PubMed

Sun, Cuixia; Wei, Yang; Li, Ruirui; Dai, Lei; Gao, Yanxiang

2017-05-17

The complexation of zein and propylene glycol alginate (PGA) was confirmed to improve the entrapment efficiency and loading capacity of quercetagetin (Q) in our previous study. The present work focused on the influence and induction mechanism of calcium ions on structures of Q-loaded zein-PGA ternary composite particles. The incorporation of Ca 2+ resulted in the formation of aggregates with a large dimension between zein particles, led to obvious conformational, secondary, and tertiary structural changes of zein, and caused the disappearance of crystalline structure of zein. PGA exhibited a fine filamentous network structure and became much thicker and stronger in the presence of Ca 2+ . The presence of Q promoted the affinity and binding capacity of Ca 2+ to zein and PGA. An interwoven network structure with enhanced firmness and density was observed in Q-loaded zein-PGA composite particles, leading to improved thermal stability. Three potential mechanisms were proposed to explain the structural characteristics induced by Ca 2+ , including particle-particle collision for zein particles, chain-chain association for PGA molecules, and simultaneous cross-linking coupled with aggregating for Q-loaded zein-PGA composite particles.

Study of zinc-induced changes in lymphocyte membranes using atomic force microscopy, luminescence, and light scattering methods

NASA Astrophysics Data System (ADS)

Filimonenko, D. S.; Khairullina, A. Ya.; Yasinskii, V. M.; Kozlova, N. M.; Zubritskaja, G. P.; Slobozhanina, E. I.

2011-07-01

Changes in the surface structure of lymphocyte membranes exposed to various concentrations of zinc ions are studied. It is found by atomic force microscopy that increasing the concentration of zinc ions leads to a reduction in the correlation length of the autocorrelation function of the roughness profile of a lymphocyte compared to control samples; this may indicate the existence of fine structure in the membrane surface. Fluorescence markers are used to observe a reduction in the microviscosity of the lipids in the outer monolayer of the lipid bilayer after lymphocytes are exposed to Zn ions, as well as the exposure of phosphatidylserine on the surface membrane, and the oxidation of HS-groups of membrane proteins. Calculations of the absorption coefficients of lymphocytes modified with zinc reveal the existence of absorption bands owing to the formation of metal-protein complexes and zinc oxide nanoparticles. These results indicate significant changes in the structural and functional state of lymphocyte membranes exposed to zinc ions.

Nonlinear nature of composite structure induced by the interaction of nonplanar solitons in a nonextensive plasma

NASA Astrophysics Data System (ADS)

Han, Jiu-Ning; Luo, Jun-Hua; Liu, Zhen-Lai; Shi, Jun; Xiang, Gen-Xiang; Li, Jun-Xiu

2015-06-01

The nonlinear properties of composite structure induced by the head-on collision of electron-acoustic solitons in a general plasma composed of cold fluid electrons, hot nonextensive distributed electron, and stationary ions are studied. We have made a detailed investigation on the time-evolution process of this merged wave structure. It is found that the structure survives during some time interval, and there are obviously different for the properties of the composite structures which are induced in cylindrical and spherical geometries. Moreover, it is shown that there are both positive and negative phase shifts for each colliding soliton after the interaction. For fixed plasma parameters, the soliton received the largest phase shift in spherical geometry, followed by the cylindrical and one-dimensional planar geometries.

Formation of SIMOX-SOI structure by high-temperature oxygen implantation

NASA Astrophysics Data System (ADS)

Hoshino, Yasushi; Kamikawa, Tomohiro; Nakata, Jyoji

2015-12-01

We have performed oxygen ion implantation in silicon at very high substrate-temperatures (⩽1000 °C) for the purpose of forming silicon-on-insulator (SOI) structure. We have expected that the high-temperature implantation can effectively avoids ion-beam-induced damages in the SOI layer and simultaneously stabilizes the buried oxide (BOX) and SOI-Si layer. Such a high-temperature implantation makes it possible to reduce the post-implantation annealing temperature. In the present study, oxygen ions with 180 keV are incident on Si(0 0 1) substrates at various temperatures from room temperature (RT) up to 1000 °C. The ion-fluencies are in order of 1017-1018 ions/cm2. Samples have been analyzed by atomic force microscope, Rutherford backscattering, and micro-Raman spectroscopy. It is found in the AFM analysis that the surface roughness of the samples implanted at 500 °C or below are significantly small with mean roughness of less than 1 nm, and gradually increased for the 800 °C-implanted sample. On the other hand, a lot of dents are observed for the 1000 °C-implanted sample. RBS analysis has revealed that stoichiometric SOI-Si and BOX-SiO2 layers are formed by oxygen implantation at the substrate temperatures of RT, 500, and 800 °C. However, SiO2-BOX layer has been desorbed during the implantation. Raman spectra shows that the ion-beam-induced damages are fairly suppressed by such a high-temperatures implantation.

Dynamic secondary ion mass spectroscopy of Au nanoparticles on Si wafer using Bi3+ as primary ion coupled with surface etching by Ar cluster ion beam: The effect of etching conditions on surface structure

NASA Astrophysics Data System (ADS)

Park, Eun Ji; Choi, Chang Min; Kim, Il Hee; Kim, Jung-Hwan; Lee, Gaehang; Jin, Jong Sung; Ganteför, Gerd; Kim, Young Dok; Choi, Myoung Choul

2018-01-01

Wet-chemically synthesized Au nanoparticles were deposited on Si wafer surfaces, and the secondary ions mass spectra (SIMS) from these samples were collected using Bi3+ with an energy of 30 keV as the primary ions. In the SIMS, Au cluster cations with a well-known, even-odd alteration pattern in the signal intensity were observed. We also performed depth profile SIMS analyses, i.e., etching the surface using an Ar gas cluster ion beam (GCIB), and a subsequent Bi3+ SIMS analysis was repetitively performed. Here, two different etching conditions (Ar1600 clusters of 10 keV energy or Ar1000 of 2.5 keV denoted as "harsh" or "soft" etching conditions, respectively) were used. Etching under harsh conditions induced emission of the Au-Si binary cluster cations in the SIMS spectra of the Bi3+ primary ions. The formation of binary cluster cations can be induced by either fragmentation of Au nanoparticles or alloying of Au and Si, increasing Au-Si coordination on the sample surface during harsh GCIB etching. Alternatively, use of the soft GCIB etching conditions resulted in exclusive emission of pure Au cluster cations with nearly no Au-Si cluster cation formation. Depth profile analyses of the Bi3+ SIMS combined with soft GCIB etching can be useful for studying the chemical environments of atoms at the surface without altering the original interface structure during etching.

Optical reflectivity study of silicon ion implanted poly(methyl methacrylate)

NASA Astrophysics Data System (ADS)

Hadjichristov, Georgi B.; Stefanov, Ivan L.; Florian, Bojana I.; Blaskova, Gergana D.; Ivanov, Victor G.; Faulques, Eric

2009-11-01

The optical reflectivity (both specular and off-specular) of poly(methyl methacrylate) (PMMA) implanted with silicon ions (Si +) at energy of 50 keV, is studied in the spectral range 0.25-25 μm. The effect from the Si + implantation on the reflectivity of two PMMA materials is examined in the dose range from 10 14 to 10 17 ions/cm 2 and is linked to the structure formed in this ion implanted plastic. As compared to the pristine PMMA, an enhancement of the reflectivity of Si + implanted PMMA is observed, that is attributed to the modification of the subsurface region of PMMA upon the ion implantation. The ion-produced subsurface organic interface is also probed by laser-induced thermo-lens.

Computational multiobjective topology optimization of silicon anode structures for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Mitchell, Sarah L.; Ortiz, Michael

2016-09-01

This study utilizes computational topology optimization methods for the systematic design of optimal multifunctional silicon anode structures for lithium-ion batteries. In order to develop next generation high performance lithium-ion batteries, key design challenges relating to the silicon anode structure must be addressed, namely the lithiation-induced mechanical degradation and the low intrinsic electrical conductivity of silicon. As such this work considers two design objectives, the first being minimum compliance under design dependent volume expansion, and the second maximum electrical conduction through the structure, both of which are subject to a constraint on material volume. Density-based topology optimization methods are employed in conjunction with regularization techniques, a continuation scheme, and mathematical programming methods. The objectives are first considered individually, during which the influence of the minimum structural feature size and prescribed volume fraction are investigated. The methodology is subsequently extended to a bi-objective formulation to simultaneously address both the structural and conduction design criteria. The weighted sum method is used to derive the Pareto fronts, which demonstrate a clear trade-off between the competing design objectives. A rigid frame structure was found to be an excellent compromise between the structural and conduction design criteria, providing both the required structural rigidity and direct conduction pathways. The developments and results presented in this work provide a foundation for the informed design and development of silicon anode structures for high performance lithium-ion batteries.

Large scale silver nanowires network fabricated by MeV hydrogen (H+) ion beam irradiation

NASA Astrophysics Data System (ADS)

Honey, S.; Naseem, S.; Ishaq, A.; Maaza, M.; Bhatti, M. T.; Wan, D.

2016-04-01

A random two-dimensional large scale nano-network of silver nanowires (Ag-NWs) is fabricated by MeV hydrogen (H+) ion beam irradiation. Ag-NWs are irradiated under H+ ion beam at different ion fluences at room temperature. The Ag-NW network is fabricated by H+ ion beam-induced welding of Ag-NWs at intersecting positions. H+ ion beam induced welding is confirmed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Moreover, the structure of Ag NWs remains stable under H+ ion beam, and networks are optically transparent. Morphology also remains stable under H+ ion beam irradiation. No slicings or cuttings of Ag-NWs are observed under MeV H+ ion beam irradiation. The results exhibit that the formation of Ag-NW network proceeds through three steps: ion beam induced thermal spikes lead to the local heating of Ag-NWs, the formation of simple junctions on small scale, and the formation of a large scale network. This observation is useful for using Ag-NWs based devices in upper space where protons are abandoned in an energy range from MeV to GeV. This high-quality Ag-NW network can also be used as a transparent electrode for optoelectronics devices. Project supported by the National Research Foundation of South Africa (NRF), the French Centre National pour la Recherche Scientifique, iThemba-LABS, the UNESCO-UNISA Africa Chair in Nanosciences & Nanotechnology, the Third World Academy of Science (TWAS), Organization of Women in Science for the Developing World (OWSDW), the Abdus Salam ICTP via the Nanosciences African Network (NANOAFNET), and the Higher Education Commission (HEC) of Pakistan.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

NASA Astrophysics Data System (ADS)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-02-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

NASA Astrophysics Data System (ADS)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-05-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Evaluation of the effect of roasting process on the energy transition and the crystalline structures of Arabica, Robusta, and Liberica coffee from Jambi Indonesia

NASA Astrophysics Data System (ADS)

Perdana, B. M.; Manihuruk, R.; Ashyar, R.; Heriyanti; Sutrisno

2018-04-01

The effect of the roasting process has been evaluated to determine of the energy transition and the crystalline structure of three types of coffee, Arabica, Robusta, and Liberica coffee both green and roasted coffee with the roasted temperature at 200°C and 230°C. The crystalline structure of the coffee was evaluated with X-ray powder diffraction (XRD). The result exposes that the three types of green coffee showed that an amorphous structure whereas the roasted coffee denotes a crystal structure of sucrose. The varied temperature in the roasting process leads to changes in the crystal structure shown by the peak shift of 2θ for all types of coffee. The added cations, such as Fe2+, Ca2+, and Mg2+ ions on Liberica coffee induced of changes in the crystal structures, which are assigned by the peak shift, that imply of metal ions of the sucrose complexes happened in the solution, except for the addition of Mg2+ ion.

Travelling-wave ion mobility and negative ion fragmentation of high mannose N-glycans

PubMed Central

Harvey, David J.; Scarff, Charlotte A.; Edgeworth, Matthew; Struwe, Weston B.; Pagel, Kevin; Thalassinos, Konstantinos; Crispin, Max; Scrivens, Jim

2016-01-01

The isomeric structure of high-mannose N-glycans can significantly impact biological recognition events. Here, the utility of travelling-wave ion mobility-mass spectrometry (TW IM-MS)for isomer separation of high-mannose N-glycans is investigated. Negative ion fragmentation using collision-induced dissociation (CID) gave more informative spectra than positive ion spectra with mass-different fragment ions characterizing many of the isomers. Isomer separation by ion mobility in both ionization modes was generally limited, with the arrival time distributions (ATD) often showing little sign of isomers. However, isomers could be partially resolved by plotting extracted fragment ATDs of the diagnostic fragment ions from the negative ion spectra and the fragmentation spectra of the isomers could be extracted by using ions from limited areas of the ATD peak. In some cases, asymmetric ATDs were observed but no isomers could be detected by fragmentation. In these cases, it was assumed that conformers were being separated. Collision cross sections (CCSs) of the isomers in positive and negative fragmentation mode were estimated from TW IM-MS data using dextran glycans as calibrant. More complete CCS data were achieved in negative ion mode by utilizing the diagnostic fragment ions. Examples of isomer separations are shown for N-glycans released from the well-characterized glycoproteins chicken ovalbumin, porcine thyroglobulin and gp120 from the human immunodeficiency virus. In addition to the cross sectional data, details of the negative ion collision-induced dissociation (CID) spectra of all resolved isomers are discussed. PMID:26956389

The structure of ions and zwitterionic lipids regulates the charge of dipolar membranes.

PubMed

Szekely, Or; Steiner, Ariel; Szekely, Pablo; Amit, Einav; Asor, Roi; Tamburu, Carmen; Raviv, Uri

2011-06-21

In pure water, zwitterionic lipids form lamellar phases with an equilibrium water gap on the order of 2 to 3 nm as a result of the dominating van der Waals attraction between dipolar bilayers. Monovalent ions can swell those neutral lamellae by a small amount. Divalent ions can adsorb onto dipolar membranes and charge them. Using solution X-ray scattering, we studied how the structure of ions and zwitterionic lipids regulates the charge of dipolar membranes. We found that unlike monovalent ions that weakly interact with all of the examined dipolar membranes, divalent and trivalent ions adsorb onto membranes containing lipids with saturated tails, with an association constant on the order of ∼10 M(-1). One double bond in the lipid tail is sufficient to prevent divalent ion adsorption. We suggest that this behavior is due to the relatively loose packing of lipids with unsaturated tails that increases the area per lipid headgroup, enabling their free rotation. Divalent ion adsorption links two lipids and limits their free rotation. The ion-dipole interaction gained by the adsorption of the ions onto unsaturated membranes is insufficient to compensate for the loss of headgroup free-rotational entropy. The ion-dipole interaction is stronger for cations with a higher valence. Nevertheless, polyamines behave as monovalent ions near dipolar interfaces in the sense that they interact weakly with the membrane surface, whereas in the bulk their behavior is similar to that of multivalent cations. Advanced data analysis and comparison with theory provide insight into the structure and interactions between ion-induced regulated charged interfaces. This study models biologically relevant interactions between cell membranes and various ions and the manner in which the lipid structure governs those interactions. The ability to monitor these interactions creates a tool for probing systems that are more complex and forms the basis for controlling the interactions between dipolar membranes and charged proteins or biopolymers for encapsulation and delivery applications. © 2011 American Chemical Society

Calcium-independent metal-ion catalytic mechanism of anthrax edema factor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yuequan; Zhukovskaya, Natalia L.; Guo, Qing

2009-11-18

Edema factor (EF), a key anthrax exotoxin, has an anthrax protective antigen-binding domain (PABD) and a calmodulin (CaM)-activated adenylyl cyclase domain. Here, we report the crystal structures of CaM-bound EF, revealing the architecture of EF PABD. CaM has N- and C-terminal domains and each domain can bind two calcium ions. Calcium binding induces the conformational change of CaM from closed to open. Structures of the EF-CaM complex show how EF locks the N-terminal domain of CaM into a closed conformation regardless of its calcium-loading state. This represents a mechanism of how CaM effector alters the calcium affinity of CaM andmore » uncouples the conformational change of CaM from calcium loading. Furthermore, structures of EF-CaM complexed with nucleotides show that EF uses two-metal-ion catalysis, a prevalent mechanism in DNA and RNA polymerases. A histidine (H351) further facilitates the catalysis of EF by activating a water to deprotonate 3'OH of ATP. Mammalian adenylyl cyclases share no structural similarity with EF and they also use two-metal-ion catalysis, suggesting the catalytic mechanism-driven convergent evolution of two structurally diverse adenylyl cyclases.« less

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

DOE PAGES

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin; ...

2018-04-26

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Laser-induced fluorescence measurements of argon and xenon ion velocities near the sheath boundary in 3 ion species plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yip, Chi-Shung; Hershkowitz, Noah; Severn, Greg

2016-05-15

The Bohm sheath criterion is studied with laser-induced fluorescence in three ion species plasmas using two tunable diode lasers. Krypton is added to a low pressure unmagnetized DC hot filament discharge in a mixture of argon and xenon gas confined by surface multi-dipole magnetic fields. The argon and xenon ion velocity distribution functions are measured at the sheath-presheath boundary near a negatively biased boundary plate. The potential structures of the plasma sheath and presheath are measured by an emissive probe. Results are compared with previous experiments with Ar–Xe plasmas, where the two ion species were observed to reach the sheathmore » edge at nearly the same speed. This speed was the ion sound speed of the system, which is consistent with the generalized Bohm criterion. In such two ion species plasmas, instability enhanced collisional friction was demonstrated [Hershkowitz et al., Phys. Plasmas 18(5), 057102 (2011).] to exist which accounted for the observed results. When three ion species are present, it is demonstrated under most circumstances the ions do not fall out of the plasma at their individual Bohm velocities. It is also shown that under most circumstances the ions do not fall out of the plasma at the system sound speed. These observations are also consistent with the presence of the instabilities.« less

Structure of Escherichia coli AdhP (ethanol-inducible dehydrogenase) with bound NAD.

PubMed

Thomas, Leonard M; Harper, Angelica R; Miner, Whitney A; Ajufo, Helen O; Branscum, Katie M; Kao, Lydia; Sims, Paul A

2013-07-01

The crystal structure of AdhP, a recombinantly expressed alcohol dehydrogenase from Escherichia coli K-12 (substrain MG1655), was determined to 2.01 Å resolution. The structure, which was solved using molecular replacement, also included the structural and catalytic zinc ions and the cofactor nicotinamide adenine dinucleotide (NAD). The crystals belonged to space group P21, with unit-cell parameters a = 68.18, b = 118.92, c = 97.87 Å, β = 106.41°. The final R factor and Rfree were 0.138 and 0.184, respectively. The structure of the active site of AdhP suggested a number of residues that may participate in a proton relay, and the overall structure of AdhP, including the coordination to structural and active-site zinc ions, is similar to those of other tetrameric alcohol dehydrogenase enzymes.

Structural derivation of lipid A from Cronobacter sakazakii using tandem mass spectrometry.

PubMed

Li, Yanyan; Yoon, Sung Hwan; Wang, Xiaoyuan; Ernst, Robert K; Goodlett, David R

2016-10-30

Cronobacter sakazakii is a Gram-negative opportunistic pathogen that can cause necrotizing enterocolitis, bacteremia, and meningitis. Lipid A, the glycolipid membrane anchor of lipopolysaccharide (LPS), is a potential virulence factor for C. sakazakii. Given the potential importance of this molecule in infection and virulence, structural characterization of lipid A was carried out. The structural characterization of lipid A extracted from C. sakazakii was performed using electrospray ionization and collision-induced dissociation in a linear ion trap mass spectrometer. Specifically, for detailed structural characterization, hierarchical tandem mass spectrometry was performed on the dominant ions present in the precursor ion mass spectra. By comparing the C. sakazakii fragmentation pathways to those of the known structure of E. coli lipid A, a structure of C. sakazakii lipid A was derived. The precursor ion at m/z 1796 from C. sakazakii is produced from a lipid A molecule where the acyl chains between the 2'b (C14) and 3'b (C12) positions are reversed as compared to E. coli lipid A. Additionally, the precursor ion at m/z 1824 from C. sakazakii corresponds to an E. coli structure with the same acyl chain at the 2'b position (C14), but a longer acyl chain (C14) at the 3'b position versus m/z 1796. Two lipid A structures were derived for the C. sakazakii ions at m/z 1796 and 1824. They differed in composition at the 2'b and 3'b acyl chain substituents, which may be a result of differences in substrate specificity of the two lipid A acyl chain transferases: LpxL and LpxM. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Theory and observation of the onset of nonlinear structures due to eigenmode destabilization by fast ions in tokamaks

DOE PAGES

Duarte, V. N.; Berk, H. L.; Gorelenkov, N. N.; ...

2017-12-12

Alfvén waves can induce the ejection of fast ions in different forms in tokamaks. In order to develop predictive capabilities to anticipate the nature of fast ion transport, a methodology is proposed to differentiate the likelihood of energetic-particle-driven instabilities to produce frequency chirping or fixed-frequency oscillations. Furthermore, the proposed method employs numerically calculated eigenstructures and multiple resonance surfaces of a given mode in the presence of energetic ion drag and stochasticity (due to collisions and micro-turbulence). Toroidicity-induced, reversed-shear and beta-induced Alfvén-acoustic eigenmodes are used as examples. Waves measured in experiments are characterized, and compatibility is found between the proposed criterionmore » predictions and the experimental observation or lack of observation of chirping behavior of Alfvénic modes in different tokamaks. It is found that the stochastic diffusion due to micro-turbulence can be the dominant energetic particle detuning mechanism near the resonances in many plasma experiments, and its strength is the key as to whether chirping solutions are likely to arise. We proposed a criterion that constitutes a useful predictive tool in assessing whether the nature of the transport for fast ion losses in fusion devices will be dominated by convective or diffusive processes.« less

Theory and observation of the onset of nonlinear structures due to eigenmode destabilization by fast ions in tokamaks

NASA Astrophysics Data System (ADS)

Duarte, V. N.; Berk, H. L.; Gorelenkov, N. N.; Heidbrink, W. W.; Kramer, G. J.; Nazikian, R.; Pace, D. C.; Podestà, M.; Van Zeeland, M. A.

2017-12-01

Alfvén waves can induce the ejection of fast ions in different forms in tokamaks. In order to develop predictive capabilities to anticipate the nature of fast ion transport, a methodology is proposed to differentiate the likelihood of energetic-particle-driven instabilities to produce frequency chirping or fixed-frequency oscillations. The proposed method employs numerically calculated eigenstructures and multiple resonance surfaces of a given mode in the presence of energetic ion drag and stochasticity (due to collisions and micro-turbulence). Toroidicity-induced, reversed-shear and beta-induced Alfvén-acoustic eigenmodes are used as examples. Waves measured in experiments are characterized, and compatibility is found between the proposed criterion predictions and the experimental observation or lack of observation of chirping behavior of Alfvénic modes in different tokamaks. It is found that the stochastic diffusion due to micro-turbulence can be the dominant energetic particle detuning mechanism near the resonances in many plasma experiments, and its strength is the key as to whether chirping solutions are likely to arise. The proposed criterion constitutes a useful predictive tool in assessing whether the nature of the transport for fast ion losses in fusion devices will be dominated by convective or diffusive processes.

Theory and observation of the onset of nonlinear structures due to eigenmode destabilization by fast ions in tokamaks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duarte, V. N.; Berk, H. L.; Gorelenkov, N. N.

Alfvén waves can induce the ejection of fast ions in different forms in tokamaks. In order to develop predictive capabilities to anticipate the nature of fast ion transport, a methodology is proposed to differentiate the likelihood of energetic-particle-driven instabilities to produce frequency chirping or fixed-frequency oscillations. Furthermore, the proposed method employs numerically calculated eigenstructures and multiple resonance surfaces of a given mode in the presence of energetic ion drag and stochasticity (due to collisions and micro-turbulence). Toroidicity-induced, reversed-shear and beta-induced Alfvén-acoustic eigenmodes are used as examples. Waves measured in experiments are characterized, and compatibility is found between the proposed criterionmore » predictions and the experimental observation or lack of observation of chirping behavior of Alfvénic modes in different tokamaks. It is found that the stochastic diffusion due to micro-turbulence can be the dominant energetic particle detuning mechanism near the resonances in many plasma experiments, and its strength is the key as to whether chirping solutions are likely to arise. We proposed a criterion that constitutes a useful predictive tool in assessing whether the nature of the transport for fast ion losses in fusion devices will be dominated by convective or diffusive processes.« less

Folding process of silk fibroin induced by ferric and ferrous ions

NASA Astrophysics Data System (ADS)

Ji, Dan; Deng, Yi-Bin; Zhou, Ping

2009-12-01

Bombyx mori silk fiber has useful mechanical properties largely due to a high content of ordered β-sheet crystallites separated by non-crystalline spacers. Metallic ions present in the silk dope in nature could affect the β-sheet content. In this work, we used solid-state 13C NMR, EPR and Raman spectroscopy to investigate how the ferric/ferrous ions affect the folding process of the silk fibroin. NMR and Raman results indicate that ferric and ferrous ions have different effects on the secondary structure of silk fibroin. Ferric ions can induce a conformation change from helix to β-sheet form in silk fibroin when their concentration exceeds a critical value, while ferrous ions cannot. EPR results indicate that the ferric ions bound with silk fibroin have a high-spin state ( S = 5/2) with g-value of g1 = 1.950, g2 = 1.990 and g3 = 1.995, zero-field splitting interaction D of 1.2-2 cm -1, and symmetric character of E/ D = 1/3, resulting in an effective g-value of g' = 4.25. The hydrophilic spacer GTGSSGFGPYVAN(H)GGYSGYEYAWSSESDFGT in the heavy chain of silk fibroin is likely to be involved in the binding of ferric ions, and His, Asn and Tyr residues are considered as the potential binding sites.

Design, synthesis and biological evaluation of multifunctional tacrine-curcumin hybrids as new cholinesterase inhibitors with metal ions-chelating and neuroprotective property.

PubMed

Liu, Zhikun; Fang, Lei; Zhang, Huan; Gou, Shaohua; Chen, Li

2017-04-15

Total sixteen tacrine-curcumin hybrid compounds were designed and synthesized for the purpose of searching for multifunctional anti-Alzheimer agents. In vitro studies showed that these hybrid compounds showed good cholinesterase inhibitory activity. Particularly, the potency of K 3-2 is even beyond tacrine. Some of the compounds exhibited different selectivity on acetylcholinesterase or butyrylcholinesterase due to the structural difference. Thus, the structure and activity relationship is summarized and further discussed based on molecular modeling studies. The ORAC and MTT assays indicated that the hybrid compounds possessed pronounced antioxidant activity and could effectively protect PC12 cells from the H 2 O 2 /Aβ42-induced toxicity. Moreover, the hybrid compounds also showed positive metal ions-chelating ability in vitro, suggesting a potential to halt ion-induced Aβ aggregation. All the obtained results demonstrated that the tacrine-curcumin hybrid compounds, in particular compound K 3-2 , can be considered as potential therapeutic agents for Alzheimer's disease. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microstructure and properties of single crystal BaTiO3 thin films synthesized by ion implantation-induced layer transfer

NASA Astrophysics Data System (ADS)

Park, Young-Bae; Ruglovsky, Jennifer L.; Atwater, Harry A.

2004-07-01

Single crystal BaTiO3 thin films have been transferred onto Pt-coated and Si3N4-coated substrates by the ion implantation-induced layer transfer method using H + and He+ ion coimplantation and subsequent annealing. The transferred BaTiO3 films are single crystalline with root mean square roughness of 17nm. Polarized optical and piezoresponse force microscopy (PFM) indicate that the BaTiO3 film domain structure closely resembles that of bulk tetragonal BaTiO3 and atomic force microscopy shows a 90° a -c domain structure with a tetragonal angle of 0.5°-0.6°. Micro-Raman spectroscopy indicates that the local mode intensity is degraded in implanted BaTiO3 but recovers during anneals above the Curie temperature. The piezoelectric coefficient, d33, is estimated from PFM to be 80-100pm/V and the coercive electric field (Ec) is 12-20kV/cm, comparable to those in single crystal BaTiO3.

Histone Deacetylase Inhibitors Prolong Cardiac Repolarization through Transcriptional Mechanisms.

PubMed

Spence, Stan; Deurinck, Mark; Ju, Haisong; Traebert, Martin; McLean, LeeAnne; Marlowe, Jennifer; Emotte, Corinne; Tritto, Elaine; Tseng, Min; Shultz, Michael; Friedrichs, Gregory S

2016-09-01

Histone deacetylase (HDAC) inhibitors are an emerging class of anticancer agents that modify gene expression by altering the acetylation status of lysine residues of histone proteins, thereby inducing transcription, cell cycle arrest, differentiation, and cell death or apoptosis of cancer cells. In the clinical setting, treatment with HDAC inhibitors has been associated with delayed cardiac repolarization and in rare instances a lethal ventricular tachyarrhythmia known as torsades de pointes. The mechanism(s) of HDAC inhibitor-induced effects on cardiac repolarization is unknown. We demonstrate that administration of structurally diverse HDAC inhibitors to dogs causes delayed but persistent increases in the heart rate corrected QT interval (QTc), an in vivo measure of cardiac repolarization, at timepoints far removed from the Tmax for parent drug and metabolites. Transcriptional profiling of ventricular myocardium from dogs treated with various HDAC inhibitors demonstrated effects on genes involved in protein trafficking, scaffolding and insertion of various ion channels into the cell membrane as well as genes for specific ion channel subunits involved in cardiac repolarization. Extensive in vitro ion channel profiling of various structural classes of HDAC inhibitors (and their major metabolites) by binding and acute patch clamp assays failed to show any consistent correlations with direct ion channel blockade. Drug-induced rescue of an intracellular trafficking-deficient mutant potassium ion channel, hERG (G601S), and decreased maturation (glycosylation) of wild-type hERG expressed by CHO cells in vitro correlated with prolongation of QTc intervals observed in vivo The results suggest that HDAC inhibitor-induced prolongation of cardiac repolarization may be mediated in part by transcriptional changes of genes required for ion channel trafficking and localization to the sarcolemma. These data have broad implications for the development of these drug classes and suggest that the optimal time to assess potentially transcriptionally mediated physiologic effects will be delayed relative to an epigenetic drug's Tmax/Cmax. © The Author 2016. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Sub-Nanosecond Lifetime Measurement Using the Recoil-Distance Method

PubMed Central

Wu, Ching-Yen

2000-01-01

The electromagnetic properties of low-lying nuclear states are a sensitive probe of both collective and single-particle degrees of freedom in nuclear structure. The recoil-distance technique provides a very reliable, direct and precise method for measuring lifetimes of nuclear states with lifetimes ranging from less than one to several hundred picoseconds. This method complements the powerful, but complicated, heavy-ion induced Coulomb excitation technique for measuring electromagnetic properties. The recoil distance technique has been combined with heavy-ion induced Coulomb excitation to study a variety of problems. Examples discussed are: study of the two-phonon triplet in 110Pd, coupling of the β and γ degrees of freedom in 182,184W, highly deformed γ bands in 165Ho, octupole collectivity in 96Zr, and opposite parity states in 153Eu. Consistency between the Coulomb excitation results and the lifetime measurements confirms the reliability of the complex analysis often encountered in heavy-ion induced Coulomb excitation work. PMID:27551588

Electric-field-induced strain effects on the magnetization of a Pr 0.67Sr 0.33MnO 3 film

DOE PAGES

Zhang, B.; Sun, C. -J.; Lu, W.; ...

2015-05-26

The electric-field control of magnetic properties of Pr 0.67Sr 0.33MnO 3 (PSMO) film on piezoelectric Pb(Mg 1/3Nb 2/3)O 3-PbTiO 3 (PMNT) substrate was investigated. The piezoelectric response of the PMNT substrate to the electric field produced strain that was coupled to the PSMO film. The in-plane compressive (tensile) strain increased (decreased) the magnetization. The change of magnetic moment was associated with the Mn ions. First principle simulations showed that the strain-induced electronic redistribution of the two e g orbitals (3d z 2 and 3d x 2 -y 2) of Mn ions was responsible for the change of magnetic moment. Thismore » work demonstrates that the magnetoelectric effect in manganite/piezoelectric hetero-structures originates from the change in eg orbital occupancy of Mn ions induced by strain rather than the interfacial effect.« less

A Secondary Structural Transition in the C-helix Promotes Gating of Cyclic Nucleotide-regulated Ion Channels*

PubMed Central

Puljung, Michael C.; Zagotta, William N.

2013-01-01

Cyclic nucleotide-regulated ion channels bind second messengers like cAMP to a C-terminal domain, consisting of a β-roll, followed by two α-helices (B- and C-helices). We monitored the cAMP-dependent changes in the structure of the C-helix of a C-terminal fragment of HCN2 channels using transition metal ion FRET between fluorophores on the C-helix and metal ions bound between histidine pairs on the same helix. cAMP induced a change in the dimensions of the C-helix and an increase in the metal binding affinity of the histidine pair. cAMP also caused an increase in the distance between a fluorophore on the C-helix and metal ions bound to the B-helix. Stabilizing the C-helix of intact CNGA1 channels by metal binding to a pair of histidines promoted channel opening. These data suggest that ordering of the C-helix is part of the gating conformational change in cyclic nucleotide-regulated channels. PMID:23525108

Ag+12 ion induced modifications of structural and optical properties of ZnO-PMMA nanocomposite films

NASA Astrophysics Data System (ADS)

Sharma, Sarla; Vyas, Rishi; Vijay, Y. K.

2013-02-01

The influence of swift heavy ion (SHI) irradiation on structural and photoluminescence (PL) properties of ZnO-PMMA nanocomposite films, prepared by solution casting method, was studied. The ZnO-PMMA nanocomposite films were irradiated using 120 MeV Ag+12 ions at different fluences varying from 1×1011 to 1×1013 ions/cm2. The intensity of the X-ray diffraction peaks is increased at the high fluence, without evolution of any new peak. A shift in absorption edge (i.e. shift in optical band gap) towards higher wavelength was observed after irradiation and PL from ZnO-PMMA nanocomposite films is found to increase up to a critical fluence and then found to be suppressed for higher fluence (1×1012 ion/cm2). The change in photoluminescence after irradiation can be attributed to the change in microstructure of PMMA matrix as well as the agglomeration of ZnO nanoparticles.

Crystal structure of metagenomic β-xylosidase/ α-l-arabinofuranosidase activated by calcium.

PubMed

Matsuzawa, Tomohiko; Kaneko, Satoshi; Kishine, Naomi; Fujimoto, Zui; Yaoi, Katsuro

2017-09-01

The crystal structure of metagenomic β-xylosidase/α-l-arabinofuranosidase CoXyl43, activated by calcium ions, was determined in its apo and complexed forms with xylotriose or l-arabinose in the presence and absence of calcium. The presence of calcium ions dramatically increases the kcat of CoXyl43 for p-nitrophenyl β-d-xylopyranoside and reduces the Michaelis constant for p-nitrophenyl α-l-arabinofuranoside. CoXyl43 consists of a single catalytic domain comprised of a five-bladed β-propeller. In the presence of calcium, a single calcium ion was observed at the centre of this catalytic domain, behind the catalytic pocket. In the absence of calcium, the calcium ion was replaced with one sodium ion and one water molecule, and the positions of these cations were shifted by 1.3 Å. The histidine-319 side chain, which coordinates to the 2-hydroxyl oxygen atom of the bound xylose molecule in the catalytic pocket, also coordinates to the calcium ion, but not to the sodium ion. The calcium-dependent increase in activity appears to be caused by the structural change in the catalytic pocket induced by the tightly bound calcium ion and coordinating water molecules, and by the protonation state of glutamic acid-268, the catalytic acid of the enzyme. Our findings further elucidate the complex relationship between metal ions and glycosidases. © The Authors 2017. Published by Oxford University Press on behalf of the Japanese Biochemical Society. All rights reserved.

The structural behavior of SrTiO3 under 400 keV Ne2+ ion irradiation

NASA Astrophysics Data System (ADS)

Su, X.; Liu, C. G.; Yang, D. Y.; Wen, J.; Fu, E. G.; Zhang, J.; Chen, L. J.; Xu, D. P.; Wang, Y. Q.; Li, Y. H.

2015-11-01

The structural behavior of polycrystalline perovskite SrTiO3 under 400 keV Ne2+ ion irradiation at both liquid nitrogen (LN2) and room temperature (RT) has been investigated. The grazing incident X-ray diffraction technique was applied to examine the radiation-induced structural evolution. The radiation behavior of SrTiO3 depends strongly on the irradiation temperature. At LN2 temperature, the samples exhibit significant lattice swelling and amorphization, whereas at RT, the lattice swelling is much less conspicuous and no amorphization is detected even at the highest irradiation dose of 5.0 dpa. Nevertheless, Ne2+ irradiation induces peak splitting in XRD patterns at both temperatures. Furthermore, first-principle calculations have been performed with VASP, involving possible defect types, to identify which defect is responsible for the radiation effect of SrTiO3. The results reveal that the oxygen vacancy defect is the most likely to contribute to the radiation behavior of SrTiO3.

Track structure based modelling of light ion radiation effects on nuclear and mitochondrial DNA

NASA Astrophysics Data System (ADS)

Schmitt, Elke; Ottolenghi, Andrea; Dingfelder, Michael; Friedland, Werner; Kundrat, Pavel; Baiocco, Giorgio

2016-07-01

Space radiation risk assessment is of great importance for manned spaceflights in order to estimate risks and to develop counter-measures to reduce them. Biophysical simulations with PARTRAC can help greatly to improve the understanding of initial biological response to ionizing radiation. Results from modelling radiation quality dependent DNA damage and repair mechanisms up to chromosomal aberrations (e.g. dicentrics) can be used to predict radiation effects depending on the kind of mixed radiation field exposure. Especially dicentric yields can serve as a biomarker for an increased risk due to radiation and hence as an indicator for the effectiveness of the used shielding. PARTRAC [1] is a multi-scale biophysical research MC code for track structure based initial DNA damage and damage response modelling. It integrates physics, radiochemistry, detailed nuclear DNA structure and molecular biology of DNA repair by NHEJ-pathway to assess radiation effects on cellular level [2]. Ongoing experiments with quasi-homogeneously distributed compared to sub-micrometre focused bunches of protons, lithium and carbon ions allow a separation of effects due to DNA damage complexity on nanometre scale from damage clustering on (sub-) micrometre scale [3, 4]. These data provide an unprecedented benchmark for the DNA damage response model in PARTRAC and help understand the mechanisms leading to cell killing and chromosomal aberrations (e.g. dicentrics) induction. A large part of space radiation is due to a mixed ion field of high energy protons and few heavier ions that can be only partly absorbed by the shielding. Radiation damage induced by low-energy ions significantly contributes to the high relative biological efficiency (RBE) of ion beams around Bragg peak regions. For slow light ions the physical cross section data basis in PARTRAC has been extended to investigate radiation quality effects in the Bragg peak region [5]. The resulting range and LET values agree with ICRU data and SRIM calculations. Preliminary studies regarding the biological endpoints DSB (cluster) and chromosomal aberrations have been performed for selected light ions up to neon. Validation with experimental data as well as further calculations are underway and final results will be presented at the meeting. Mitochondrial alterations have been implicated in radiation-induced cardiovascular effects. To extend the applicability of PARTRAC biophysical tool towards effects on mitochondria, the nuclear DNA and chromatin as the primary target of radiation has been complemented by a model of mitochondrial DNA (mtDNA) to mimic a coronary cell with thousand mitochondria contained in the cytoplasm. Induced mtDNA damage (SSB, DSB) has been scored for 60Co photons and 5 MeV alpha-particle irradiation, assuming alternative radical scavenging capacities within the mitochondria. While direct radiation effects in mtDNA are identical to nuclear DNA, indirect effects in mtDNA are in general larger due to lower scavenging and the lack of DNA-protecting histones. These simulations complement the scarce experimental data on radiation-induced mtDNA damage and help elucidate the relative roles of initial mtDNA versus nuclear DNA damage and of pathways that amplify their respective effects. Ongoing and planned developments of PARTRAC include coupling with a radiation transport code and track-structure based calculations of cell killing for RBE studies on macroscopic scales within a mixed ion field. [1] Friedland, Dingfelder et al. (2011): "Track structures, DNA targets and radiation effects in the biophysical Monte Carlo simulation code PARTRAC", Mutat. Res. 711, 28-40 [2] Friedland et al. (2013): "Track structure based modelling of chromosome aberrations after photon and alpha-particle irradiation", Mutat. Res. 756, 213-223 [3] Schmid, Friedland et al. (2015): "Sub-micrometer 20 MeV protons or 45 MeV lithium spot irradiation enhances yields of dicentric chromosomes due to clustering of DNA double-strand breaks", Mutat. Res. 793, 30-40 [4] Friedland, Schmitt, Kundrat (2015): "Modelling Proton bunches focussed to submicrometre scales: Low-LET Radiation damage in high-LET-like spatial structure", Radiat. Prot. Dosim. 166, 34-37 [5] Schmitt, Friedland, Kundrat, Dingfelder, Ottolenghi (2015): "Cross section scaling for track structure simulations of low-energy ions in liquid water", Radiat. Prot. Dosim. 166, 15-18} Supported by the European Atomic Energy Community's Seventh Framework Programme (FP7/2007-2011) under grant agreement no 249689 "DoReMi" and the German Federal Ministry on Education and Research (KVSF-Projekt "LET-Verbund").

Standardization of accelerator irradiation procedures for simulation of neutron induced damage in reactor structural materials

NASA Astrophysics Data System (ADS)

Shao, Lin; Gigax, Jonathan; Chen, Di; Kim, Hyosim; Garner, Frank A.; Wang, Jing; Toloczko, Mychailo B.

2017-10-01

Self-ion irradiation is widely used as a method to simulate neutron damage in reactor structural materials. Accelerator-based simulation of void swelling, however, introduces a number of neutron-atypical features which require careful data extraction and, in some cases, introduction of innovative irradiation techniques to alleviate these issues. We briefly summarize three such atypical features: defect imbalance effects, pulsed beam effects, and carbon contamination. The latter issue has just been recently recognized as being relevant to simulation of void swelling and is discussed here in greater detail. It is shown that carbon ions are entrained in the ion beam by Coulomb force drag and accelerated toward the target surface. Beam-contaminant interactions are modeled using molecular dynamics simulation. By applying a multiple beam deflection technique, carbon and other contaminants can be effectively filtered out, as demonstrated in an irradiation of HT-9 alloy by 3.5 MeV Fe ions.

Competing Structural Instabilities in the Ruddlesden–Popper Derivatives HRTiO 4 (R = Rare Earths): Oxygen Octahedral Rotations Inducing Noncentrosymmetricity and Layer Sliding Retaining Centrosymmetricity

DOE PAGES

Sen Gupta, Arnab; Akamatsu, Hirofumi; Brown, Forrest G.; ...

2016-12-06

We report the discovery of noncentrosymmetry in the family of HRTiO 4 (R = Eu, Gd, Dy) layered oxides possessing a Ruddlesden-Popper derivative structure, by second harmonic generation and synchrotron x-ray diffraction with the support of density functional theory calculations. These oxides were previously thought to possess inversion symmetry. Here, inversion symmetry is broken by oxygen octahedral rotations, a mechanism that is not active in simple perovskites. We discover a competition between oxygen octahedral rotations and sliding of the octahedral perovskite blocks at the OH layers. For the smaller rare earth ions, R = Eu, Gd, Dy, which favor themore » octahedral rotations, noncentrosymmetry is present but the sliding at the OH layer is absent. For the larger rare earth ions, R = Nd and Sm, the octahe-dral rotations are absent, but sliding of the octahedral blocks at the OH layer is present, likely to optimize the hydrogen bond length arising from the directional nature of these bonds in the crystal structure. The study reveals a new mechanism for inducing noncentrosymmetry in layered oxides, and chemical-structural effects related to rare earth ion size and hydrogen bonding that can turn this mechanism on and off. In conclusion, we construct a complete phase diagram of temperature versus rare earth ionic radius for the HRTiO 4 family.« less

Competing Structural Instabilities in the Ruddlesden–Popper Derivatives HRTiO 4 (R = Rare Earths): Oxygen Octahedral Rotations Inducing Noncentrosymmetricity and Layer Sliding Retaining Centrosymmetricity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sen Gupta, Arnab; Akamatsu, Hirofumi; Brown, Forrest G.

We report the discovery of noncentrosymmetry in the family of HRTiO 4 (R = Eu, Gd, Dy) layered oxides possessing a Ruddlesden-Popper derivative structure, by second harmonic generation and synchrotron x-ray diffraction with the support of density functional theory calculations. These oxides were previously thought to possess inversion symmetry. Here, inversion symmetry is broken by oxygen octahedral rotations, a mechanism that is not active in simple perovskites. We discover a competition between oxygen octahedral rotations and sliding of the octahedral perovskite blocks at the OH layers. For the smaller rare earth ions, R = Eu, Gd, Dy, which favor themore » octahedral rotations, noncentrosymmetry is present but the sliding at the OH layer is absent. For the larger rare earth ions, R = Nd and Sm, the octahe-dral rotations are absent, but sliding of the octahedral blocks at the OH layer is present, likely to optimize the hydrogen bond length arising from the directional nature of these bonds in the crystal structure. The study reveals a new mechanism for inducing noncentrosymmetry in layered oxides, and chemical-structural effects related to rare earth ion size and hydrogen bonding that can turn this mechanism on and off. In conclusion, we construct a complete phase diagram of temperature versus rare earth ionic radius for the HRTiO 4 family.« less

Tuning the Outward to Inward Swelling in Lithiated Silicon Nanotubes via Surface Oxide Coating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jiangwei; Luo, Hao; Liu, Yang

2016-09-14

The electrochemically-induced mechanical degradation hinders the application of Si anodes in advanced lithium-ion batteries. Hollow structures and surface coatings have been often used to mitigate the degradation of Si-based anodes. However, the structural change and degradation mechanism during lithiation/delithiation of hollow Si structures with coatings remain unclear. Here, we combine in situ TEM experiment and chemomechanical modeling to study the electrochemically induced swelling of amorphous-Si (a-Si) nanotubes with different thicknesses of surface SiOx layers. Surprisingly, we find that no inward expansion occurs at the inner surface during lithiation of a-Si nanotubes with native oxides. In contrast, inward expansion can bemore » induced by increasing the thickness of SiOx on the outer surface. Moreover, both the sandwich lithiation mechanism and two-stage lithiation process in a-Si nanotubes remain unchanged with the increasing thickness of surface coatings. Our chemomechanical modeling reveals the mechanical confinement effects in lithiated a-Si nanotubes with and without SiOx coatings. This work not only provides insights into the degradation of nanotube anodes with surface coatings, but also sheds light onto the optimal design of hollow anodes for high-performance lithium-ion batteries.« less

Stability of nano-scaled Ta/Ti multilayers upon argon ion irradiation

NASA Astrophysics Data System (ADS)

Milosavljević, M.; Milinović, V.; Peruško, D.; Grce, A.; Stojanović, M.; Pjević, D.; Mitrić, M.; Kovač, J.; Homewood, K. P.

2011-10-01

The effects of argon ion irradiation on structural changes in Ta/Ti multilayers deposited on Si wafers were investigated. The starting structures consisted of sputter deposited 10 alternate Ta (˜23 nm) and Ti (˜17 nm) layers of a total thickness ˜200 nm. They were irradiated at room temperature with 200 keV Ar +, to the fluences from 5 × 10 15 to 2 × 10 16 ions/cm 2. The projected ion range was around mid-depth of the multilayered structure, and maximum displacements per atom ˜130. It was found that, despite of the relatively heavy ion irradiation, individual nanocrystalline Ta and Ti layers remain unmixed, keeping the same level of interface planarity. The changes observed in the mostly affected region are increase in lateral dimensions of crystal grains in individual layers, and incorporation of bubbles and defects that cause some stretching of the crystal lattice. Absence of interlayer mixing is assigned to Ta-Ti immiscibility (reaction enthalpy Δ H f = +2 kJ/mol). It is estimated that up to ˜5 at.% interface mixing induced directly by collision cascades could be compensated by dynamic demixing due to chemical driving forces in the temperature relaxation regime. The results can be interesting towards developing radiation tolerant materials based on multilayered structures.

Kinetic feature of dipolarization fronts produced by interchange instability in the magnetotail

NASA Astrophysics Data System (ADS)

Lyu, Haoyu

2017-04-01

A two-dimensional extended MHD simulation is performed to study the kinetic feature of depolarization fronts (DF) in the scale of the ion inertial length / ion Larmor radius. The interchange instability, arising due to the force imbalance between the tailward gradient of thermal pressure and Earthward magnetic curvature force, self-consistently produces the DF in the near-Earth region. Numerical investigations indicate that the DF is a tangential discontinuity, which means that the normal plasma velocity across the DF should be zero in the reference system that is static with the DF structure. The electric system, including electric field and current, is determined by Hall effect arising in the scale of ion inertial length. Hall effect not only mainly contributes on the electric field normal to the tangent plane of the DF, increases the current along the tangent plane of the DF, but also makes the DF structure asymmetric. The drifting motion of the large-scale DF structure is determined by the FLR effect arising in the scale of ion Larmor radius. The ion magnetization velocity induced by the FLR effect is towards to duskward at the subsolar point of the DF, but the y component of velocity in the region after the DF, which dominantly results in the drifting motion of the whole mushroom structure towards the dawn.

Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brettmann, Blair; Pincus, Philip; Tirrell, Matthew

2017-01-13

We provide a theoretical model for the collapse of polyelectrolyte brushes in the presence of multivalent ions, focusing on the formation of lateral inhomogeneties in the collapsed state. Polyelectrolyte brushes are important in a variety of applications, including stabilizing colloidal particles and lubricating surfaces. Many uses rely on the extension of the densely grafted polymer chains from the surface in the extended brush morphology. In the presence Extended Brush of multivalent ions, brushes are significantly shorter than in monovalent ionic solutions, which greatly affects their properties. We base our theoretical analysis on an analogous collapse of polyelectrolyte brushes in amore » poor solvent, providing an energy balance representation for pinned micelles and cylindrical bundles. The equilibrium brush heights predicted for these structures are of a similar magnitude to those measured experimentally. The formation of lateral structures can open new avenues for stimuli-responsive applications that rely on nanoscale pattern formation on surfaces.« less

Inducing superconductivity in Weyl semimetal microstructures by selective ion sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bachmann, Maja D.; Nair, Nityan; Flicker, Felix

By introducing a superconducting gap in Weyl or Dirac semimetals, the superconducting state inherits the nontrivial topology of their electronic structure. As a result, Weyl superconductors are expected to host exotic phenomena, such as nonzero-momentum pairing due to their chiral node structure, or zero-energy Majorana modes at the surface. These are of fundamental interest to improve our understanding of correlated topological systems, and, moreover, practical applications in phase-coherent devices and quantum applications have been proposed. Proximity-induced superconductivity promises to allow these experiments on nonsuperconducting Weyl semimetals. Here, we show a new route to reliably fabricate superconducting microstructures from the nonsuperconductingmore » Weyl semimetal NbAs under ion irradiation. Furthermore, the significant difference in the surface binding energy of Nb and As leads to a natural enrichment of Nb at the surface during ion milling, forming a superconducting surface layer (Tc ~ 3.5 K). Being formed from the target crystal itself, the ideal contact between the superconductor and the bulk may enable an effective gapping of the Weyl nodes in the bulk because of the proximity effect. Simple ion irradiation may thus serve as a powerful tool for the fabrication of topological quantum devices from monoarsenides, even on an industrial scale.« less

Ag implantation-induced modification of Ni-Ti shape memory alloy thin films

NASA Astrophysics Data System (ADS)

Kumar, V.; Singhal, R.; Vishnoi, R.; Banerjee, M. K.; Sharma, M. C.; Asokan, K.; Kumar, M.

2017-08-01

Nanocrystalline thin films of Ni-Ti shape memory alloy are deposited on an Si substrate by the DC-magnetron co-sputtering technique and 120 keV Ag ions are implanted at different fluences. The thickness and composition of the pristine films are determined by Rutherford Backscattering Spectrometry (RBS). X-Ray diffraction (XRD), atomic force microscopy (AFM) and four-point probe resistivity methods have been used to study the structural, morphological and electrical transport properties. XRD analysis has revealed the existence of martensitic and austenite phases in the pristine film and also evidenced the structural changes in Ag-implanted Ni-Ti films at different fluences. AFM studies have revealed that surface roughness and grain size of Ni-Ti films have decreased with an increase in ion fluence. The modifications in the mechanical behaviour of implanted Ni-Ti films w.r.t pristine film is determined by using a Nano-indentation tester at room temperature. Higher hardness and the ratio of higher hardness (H) to elastic modulus (Er) are observed for the film implanted at an optimized fluence of 9 × 1015 ions/cm2. This improvement in mechanical behaviour could be understood in terms of grain refinement and dislocation induced by the Ag ion implantation in the Ni-Ti thin films.

HREM study of irradiation damage in human dental enamel crystals.

PubMed

Brès, E F; Hutchison, J L; Senger, B; Voegel, J C; Frank, R M

1991-06-01

Several phenomena have been observed during the examination of human dental enamel crystals (mainly constituted by hydroxyapatite (OHAP] by high-resolution electron microscopy (HREM) at 300 and 400 keV: orientation-dependent damage in the form of mass loss from voids or uniform destruction of crystal structure, beam-induced diffusion creating outgrowths at the crystal surfaces, recrystallization of the bulk crystal and crystallization of the inorganic components of the matrix surrounding the crystals. These beam-induced crystals have the CaO structure. The phenomena observed are most likely due to various electron-crystal interaction mechanisms (ballistic knock-on damage, electronic excitations, temperature rise, etc.). In this paper, the contribution of the ballistic process to the phenomena observed is discussed. The quantitative description of the knock-on collisions rests on the McKinley-Feshbach cross-section formula. The minimum ion displacement energies which appear in this expression have been estimated on the basis of the electrostatic ion binding energies, and the covalent bond energies if required. It is shown that hydroxyl, calcium and oxygen ions can effectively be displaced by the incident 300 and 400 keV electrons. Thus, the formation of CaO crystals by the combination of calcium and oxygen ions diffusing from their initial sites inside the OHAP lattice can tentatively be explained.

Inducing superconductivity in Weyl semimetal microstructures by selective ion sputtering

DOE PAGES

Bachmann, Maja D.; Nair, Nityan; Flicker, Felix; ...

2017-05-24

By introducing a superconducting gap in Weyl or Dirac semimetals, the superconducting state inherits the nontrivial topology of their electronic structure. As a result, Weyl superconductors are expected to host exotic phenomena, such as nonzero-momentum pairing due to their chiral node structure, or zero-energy Majorana modes at the surface. These are of fundamental interest to improve our understanding of correlated topological systems, and, moreover, practical applications in phase-coherent devices and quantum applications have been proposed. Proximity-induced superconductivity promises to allow these experiments on nonsuperconducting Weyl semimetals. Here, we show a new route to reliably fabricate superconducting microstructures from the nonsuperconductingmore » Weyl semimetal NbAs under ion irradiation. Furthermore, the significant difference in the surface binding energy of Nb and As leads to a natural enrichment of Nb at the surface during ion milling, forming a superconducting surface layer (Tc ~ 3.5 K). Being formed from the target crystal itself, the ideal contact between the superconductor and the bulk may enable an effective gapping of the Weyl nodes in the bulk because of the proximity effect. Simple ion irradiation may thus serve as a powerful tool for the fabrication of topological quantum devices from monoarsenides, even on an industrial scale.« less

Mass spectrometry of analytical derivatives. 2. "Ortho" and "Para" effects in electron ionization mass spectra of derivatives of hydroxy, mercapto and amino benzoic acids.

PubMed

Todua, Nino G; Mikaia, Anzor I

2016-01-01

Derivatives requiring either anhydrous or aqueous reaction conditions were prepared for robust and reliable gas chromatography/mass spectrometry (GC/MS) characterization of hydroxyl, mercapto, and amino benzoic acids Methylation and trialkylsilytation are employed for blocking the acidic function. Alkyl, trimethylsilyl, acetyl, perfluoroacyl and alkoxycarbonyl derivatization groups are introduced to hydroxyl, mercapto and amino functions. The electron ionization induced fragmentation characteristics of corresponding derivatives are explained by comparing the MS 1 spectra of unlabeled compounds to their 2 H and 13 C labeled analogs, and analysis of collision-induced dissociation data from MS 2 spectra. Competing fragmentation alternatives are identified and specific decomposition processes are detailed that characterize (a) ortho isomers due to interaction or vicinal functional substituents and (b) para isomers prone to forming para quinoid type structures. Skeletal and hydrogen rearrangements typical for methyl benzoates and the blocking groups are considered when discussing diagnostically important ions. Characteristic ions produced as a result of rearrangements in ortho isomers are classified, and skeletal rearrangements required to produce para quinoid type ions specific for para isomers are noted. Key ions for structure elucidation and differentiation of isomers for derivatives of substituted benzoic acids by GC/MS are suggested.

Mass spectrometry of analytical derivatives. 2. “Ortho” and “Para” effects in electron ionization mass spectra of derivatives of hydroxy, mercapto and amino benzoic acids1

PubMed Central

Todua, Nino G.; Mikaia, Anzor I.

2016-01-01

Derivatives requiring either anhydrous or aqueous reaction conditions were prepared for robust and reliable gas chromatography/mass spectrometry (GC/MS) characterization of hydroxyl, mercapto, and amino benzoic acids Methylation and trialkylsilytation are employed for blocking the acidic function. Alkyl, trimethylsilyl, acetyl, perfluoroacyl and alkoxycarbonyl derivatization groups are introduced to hydroxyl, mercapto and amino functions. The electron ionization induced fragmentation characteristics of corresponding derivatives are explained by comparing the MS1 spectra of unlabeled compounds to their 2H and 13C labeled analogs, and analysis of collision-induced dissociation data from MS2 spectra. Competing fragmentation alternatives are identified and specific decomposition processes are detailed that characterize (a) ortho isomers due to interaction or vicinal functional substituents and (b) para isomers prone to forming para quinoid type structures. Skeletal and hydrogen rearrangements typical for methyl benzoates and the blocking groups are considered when discussing diagnostically important ions. Characteristic ions produced as a result of rearrangements in ortho isomers are classified, and skeletal rearrangements required to produce para quinoid type ions specific for para isomers are noted. Key ions for structure elucidation and differentiation of isomers for derivatives of substituted benzoic acids by GC/MS are suggested. PMID:27891187

Use of terbium as a probe of tRNA tertiary structure and folding.

PubMed Central

Hargittai, M R; Musier-Forsyth, K

2000-01-01

Lanthanide metals such as terbium have previously been shown to be useful for mapping metal-binding sites in RNA. Terbium binds to the same sites on RNA as magnesium, however, with a much higher affinity. Thus, low concentrations of terbium ions can easily displace magnesium and promote phosphodiester backbone scission. At higher concentrations, terbium cleaves RNA in a sequence-independent manner, with a preference for single-stranded, non-Watson-Crick base-paired regions. Here, we show that terbium is a sensitive probe of human tRNALys,3 tertiary structure and folding. When 1 microM tRNA is used, the optimal terbium ion concentration for detecting Mg2+-induced tertiary structural changes is 50-60 microM. Using these concentrations of RNA and terbium, a magnesium-dependent folding transition with a midpoint (KMg) of 2.6 mM is observed for unmodified human tRNALys,3. At lower Tb3+ concentrations, cleavage is restricted to nucleotides that constitute specific metal-binding pockets. This small chemical probe should also be useful for detecting protein induced structural changes in RNA. PMID:11105765

Laser-stimulated electric quadrupole transitions in the molecular hydrogen ion H2+

NASA Astrophysics Data System (ADS)

Korobov, V. I.; Danev, P.; Bakalov, D.; Schiller, S.

2018-03-01

Molecular hydrogen ions are of metrological relevance due to the possibility of precise theoretical evaluation of their spectrum and of external-field-induced shifts. We report the results of the calculations of the rate of laser-induced electric quadrupole transitions between a large set of ro-vibrational states of H2+. The hyperfine and Zeeman structure of the E 2 transition spectrum and the effects of the laser polarization are treated in detail. The treatment is generally applicable to molecules in 2Σ states. We also present the nuclear spin-electron spin-coupling constants, computed with a precision ten times higher than previously obtained.

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

DOE PAGES

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta; ...

2017-04-17

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Induced in-source fragmentation pattern of certain novel (1Z,2E)-N-(aryl)propanehydrazonoyl chlorides by electrospray mass spectrometry (ESI-MS/MS)

PubMed Central

2013-01-01

Background Collision induced dissociation (CID) in the triple quadrupole mass spectrometer system (QQQ) typically yields more abundant fragment ions than those produced with resonance excitation in the presence of helium gas in the ion trap mass spectrometer system (IT). Detailed product ion spectra can be obtained from one stage MS2 scan using the QQQ. In contrast, generating the same number of fragment ions in the ion trap requires multiple stages of fragmentation (MSn) using CID via in-trap resonance excitation with the associated time penalties and drop in sensitivity. Results The use of in-source fragmentation with electrospray ionization (ESI) followed by product ion scan (MS2) in a triple quadrupole mass spectrometer system, was demonstrated. This process enhances the qualitative power of tandem mass spectrometry to simulate the MS3 of ion trap for a comprehensive study of fragmentation mechanisms. A five pharmacologically significant (1Z, 2E)-N-arylpropanehydrazonoyl chlorides (3a-e) were chosen as model compounds for this study. In this work, detailed fragmentation pathways were elucidated by further dissociation of each fragment ion in the ion spectrum, essentially, by incorporating fragmentor voltage induced dissociation (in-source fragmentation) and isolation of fragments in a quadrupole cell Q1. Subsequently, CID occurs in cell, Q2, and fragment ions are analyzed in Q3 operated in product ion mode this process can be referred to as pseudo-MS3 scan mode. Conclusions This approach allowed unambiguous assignment of all fragment ions using tandem mass spectrometer and provided adequate sensitivity and selectivity. It is beneficial for structure determination of unknown trace components. The data presented in this paper provide useful information on the effect of different substituents on the ionization/fragmentation processes and can be used in the characterization of this important class of compounds. PMID:23351484

Anti-ulcer agents: chemical aspect of solving the problem

NASA Astrophysics Data System (ADS)

Rogoza, L. N.; Salakhutdinov, N. F.

2015-01-01

The data on chemical structures and specific activities of compounds functioning as histamine H2-receptor antagonists, H+/K+-ATPase inhibitors at the exchange sites of hydrogen ions (proton pump inhibitors) and potassium ions (K+-competitive acid blockers) published from 1990 to 2013 are surveyed. The antisecretory agents with studied cytoprotective activity or with additional therapeutic properties compensating for disorders of internal defence mechanisms are presented. A separate section is devoted to the drugs that prevent or mitigate the NSAID-induced intestinal damage. All of the considered structures are classified according to the type of biological mechanism of action. Some aspects of the structure-activity relationships for such compounds are considered. The bibliography includes 83 references.

Modeling of intense pulsed ion beam heated masked targets for extreme materials characterization

DOE PAGES

Barnard, John J.; Schenkel, Thomas

2017-11-15

Intense, pulsed ion beams locally heat materials and deliver dense electronic excitations that can induce material modifications and phase transitions. Material properties can potentially be stabilized by rapid quenching. Pulsed ion beams with pulse lengths of order ns have recently become available for materials processing. Here, we optimize mask geometries for local modification of materials by intense ion pulses. The goal is to rapidly excite targets volumetrically to the point where a phase transition or local lattice reconstruction is induced followed by rapid cooling that stabilizes desired material's properties fast enough before the target is altered or damaged by, e.g.,more » hydrodynamic expansion. By using a mask, the longitudinal dimension can be large compared to the transverse dimension, allowing the possibility of rapid transverse cooling. We performed HYDRA simulations that calculate peak temperatures for a series of excitation conditions and cooling rates of silicon targets with micro-structured masks and compare these to a simple analytical model. In conclusion, the model gives scaling laws that can guide the design of targets over a wide range of pulsed ion beam parameters.« less

Metal/Ion Interactions Induced p–i–n Junction in Methylammonium Lead Triiodide Perovskite Single Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Ting; Mukherjee, Rupam; Ovchinnikova, Olga S.

Hybrid perovskites, as emerging multifunctional semiconductors, have demonstrated dual electronic/ionic conduction properties. Here, we report a metal/ion interaction induced p-i-n junction across slightly n-type doped MAPbI 3 single crystals with Au/MAPbI 3/Ag configuration based on interface dependent Seebeck effect, Hall effect and time-of-flight secondary ion mass spectrometry analysis. The organic cations (MA +) interact with Au atoms, forming positively charged coordination complexes at Au/MAPbI 3 interface, whereas iodine anions (I –) can react with Ag contacts, leading to interfacial ionic polarization. Such metal/ion interactions establish a p-doped region near the Au/MAPbI 3 interface due to the formation of MA +more » vacancies, and an n-doped region near the Ag/MAPbI 3 interface due to formation of I – vacancies, consequently forming a p-i-n junction across the crystal in Au/MAPbI 3/Ag configuration. Therefore, the metal/ion interaction plays a role in determining the surface electronic structure and semiconducting properties of hybrid perovskites.« less

Modeling of intense pulsed ion beam heated masked targets for extreme materials characterization

NASA Astrophysics Data System (ADS)

Barnard, John J.; Schenkel, Thomas

2017-11-01

Intense, pulsed ion beams locally heat materials and deliver dense electronic excitations that can induce material modifications and phase transitions. Material properties can potentially be stabilized by rapid quenching. Pulsed ion beams with pulse lengths of order ns have recently become available for materials processing. Here, we optimize mask geometries for local modification of materials by intense ion pulses. The goal is to rapidly excite targets volumetrically to the point where a phase transition or local lattice reconstruction is induced followed by rapid cooling that stabilizes desired material's properties fast enough before the target is altered or damaged by, e.g., hydrodynamic expansion. By using a mask, the longitudinal dimension can be large compared to the transverse dimension, allowing the possibility of rapid transverse cooling. We performed HYDRA simulations that calculate peak temperatures for a series of excitation conditions and cooling rates of silicon targets with micro-structured masks and compare these to a simple analytical model. The model gives scaling laws that can guide the design of targets over a wide range of pulsed ion beam parameters.

Metal/Ion Interactions Induced p–i–n Junction in Methylammonium Lead Triiodide Perovskite Single Crystals

DOE PAGES

Wu, Ting; Mukherjee, Rupam; Ovchinnikova, Olga S.; ...

2017-11-17

Hybrid perovskites, as emerging multifunctional semiconductors, have demonstrated dual electronic/ionic conduction properties. Here, we report a metal/ion interaction induced p-i-n junction across slightly n-type doped MAPbI 3 single crystals with Au/MAPbI 3/Ag configuration based on interface dependent Seebeck effect, Hall effect and time-of-flight secondary ion mass spectrometry analysis. The organic cations (MA +) interact with Au atoms, forming positively charged coordination complexes at Au/MAPbI 3 interface, whereas iodine anions (I –) can react with Ag contacts, leading to interfacial ionic polarization. Such metal/ion interactions establish a p-doped region near the Au/MAPbI 3 interface due to the formation of MA +more » vacancies, and an n-doped region near the Ag/MAPbI 3 interface due to formation of I – vacancies, consequently forming a p-i-n junction across the crystal in Au/MAPbI 3/Ag configuration. Therefore, the metal/ion interaction plays a role in determining the surface electronic structure and semiconducting properties of hybrid perovskites.« less

A magnesium-induced triplex pre-organizes the SAM-II riboswitch

PubMed Central

Roy, Susmita; Lammert, Heiko; Dayie, T. Kwaku; Sanbonmatsu, Karissa Y.

2017-01-01

Our 13C- and 1H-chemical exchange saturation transfer (CEST) experiments previously revealed a dynamic exchange between partially closed and open conformations of the SAM-II riboswitch in the absence of ligand. Here, all-atom structure-based molecular simulations, with the electrostatic effects of Manning counter-ion condensation and explicit magnesium ions are employed to calculate the folding free energy landscape of the SAM-II riboswitch. We use this analysis to predict that magnesium ions remodel the landscape, shifting the equilibrium away from the extended, partially unfolded state towards a compact, pre-organized conformation that resembles the ligand-bound state. Our CEST and SAXS experiments, at different magnesium ion concentrations, quantitatively confirm our simulation results, demonstrating that magnesium ions induce collapse and pre-organization. Agreement between theory and experiment bolsters microscopic interpretation of our simulations, which shows that triplex formation between helix P2b and loop L1 is highly sensitive to magnesium and plays a key role in pre-organization. Pre-organization of the SAM-II riboswitch allows rapid detection of ligand with high selectivity, which is important for biological function. PMID:28248966

Formation of silicon nanodots via ion beam sputtering of ultrathin gold thin film coatings on Si

PubMed Central

2011-01-01

Ion beam sputtering of ultrathin film Au coatings used as a physical catalyst for self-organization of Si nanostructures has been achieved by tuning the incident particle energy. This approach holds promise as a scalable nanomanufacturing parallel processing alternative to candidate nanolithography techniques. Structures of 11- to 14-nm Si nanodots are formed with normal incidence low-energy Ar ions of 200 eV and fluences above 2 × 1017 cm-2. In situ surface characterization during ion irradiation elucidates early stage ion mixing migration mechanism for nanodot self-organization. In particular, the evolution from gold film islands to the formation of ion-induced metastable gold silicide followed by pure Si nanodots formed with no need for impurity seeding. PMID:21711934

Ion irradiation of electronic-type-separated single wall carbon nanotubes: A model for radiation effects in nanostructured carbon

NASA Astrophysics Data System (ADS)

Rossi, Jamie E.; Cress, Cory D.; Helenic, Alysha R.; Schauerman, Chris M.; DiLeo, Roberta A.; Cox, Nathanael D.; Messenger, Scott R.; Weaver, Brad D.; Hubbard, Seth M.; Landi, Brian J.

2012-08-01

The structural and electrical properties of electronic-type-separated (metallic and semiconducting) single wall carbon nanotube (SWCNT) thin-films have been investigated after irradiation with 150 keV 11B+ and 150 keV 31P+ with fluences ranging from 1012 to 1015 ions/cm2. Raman spectroscopy results indicate that the ratio of the Raman D to G' band peak intensities (D/G') is a more sensitive indicator of SWCNT structural modification induced by ion irradiation by one order of magnitude compared to the ratio of the Raman D to G band peak intensities (D/G). The increase in sheet resistance (Rs) of the thin-films follows a similar trend as the D/G' ratio, suggesting that the radiation induced variation in bulk electrical transport for both electronic-types is equal and related to localized defect generation. The characterization results for the various samples are compared based on the displacement damage dose (DDD) imparted to the sample, which is material and damage source independent. Therefore, it is possible to extend the analysis to include data from irradiation of transferred CVD-graphene films on SiO2/Si substrates using 35 keV C+ ions, and compare the observed changes at equivalent levels of ion irradiation-induced damage to that observed in the SWCNT thin-film samples. Ultimately, a model is developed for the prediction of the radiation response of nanostructured carbon materials based on the DDD for any incident ion with low-energy recoil spectra. The model is also related to the defect concentration, and subsequently the effective defect-to-defect length, and yields a maximum defect concentration (minimum defect-to-defect length) above which the bulk electrical transport properties in SWCNT thin-films and large graphene-based electronic devices rapidly degrade when exposed to harsh environments.

A spectroscopic ellispometric study of the tunability of the optical constants and thickness of GeO{sub x} films with swift heavy ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayarangamuthu, K.; Singh, Chaman; Rath, Shyama

2011-09-15

Sub-stoichiometric GeO{sub x} films were fabricated by electron-beam evaporation method. The films were irradiated with 100 MeV Ag{sup 7+} ions at fluences between 1 x 10{sup 12} and 1 x 10{sup 14} ions-cm{sup -2}. Spectroscopic ellipsometric measurements were performed in air at room temperature. The values of the layer thickness and refractive index were extracted from ellipsometry using a multilayer analysis and the Tauc Lorentz model. The refractive index (at 633 nm) of the as-deposited GeO{sub x} film was estimated to be 1.860 and decreased to 1.823 for films irradiated at an ion fluence of 1 x 10{sup 14} ions-cm{supmore » -2}. The thickness of the films also decreased after irradiation and is due to a sputtering induced by the ion beam. The change in the refractive index with ion fluence is attributed to a stoichiometric change and structural transformation represented by GeO{sub x}{yields} Ge + GeO{sub y} (y > x) occurring due to a thermal spike induced by ion irradiation. Swift heavy ions thus provide a scope for modulating the refractive index of GeO{sub x} films. The thickness and stoichiometric changes are supported by Rutherford backscattering measurements.« less

Induction of relaxor state in ordinary ferroelectrics by isovalent ion substitution: A pretransitional martensitic texture case

NASA Astrophysics Data System (ADS)

Lente, M. H.; Moreira, E. N.; Garcia, D.; Eiras, J. A.; Neves, P. P.; Doriguetto, A. C.; Mastelaro, V. R.; Mascarenhas, Y. P.

2006-02-01

The understanding of the structural origin of relaxor ferroelectrics has been doubtlessly a long-standing puzzle in the field of ferroelectricity. Thus, motivated by the interest in improving the comprehension of this important issue, it a framework is proposed for explaining the origin of the relaxor state in ordinary ferroelectrics induced via the isovalent-ion substitution. Based on the martensitic transformation concepts, it is proposed that the continuous addition of isovalent ions in a so-called normal ferroelectric decreases considerably the elastic strain energy. This results in a gradual transformation of ferroelectric domain patterns from a micrometer polydomain structure (twins), through single domains, to nanometer-polar-“tweed” structures with glasslike behavior, that are, in turn, strongly driven by point defects and surface effects. The electrical interaction between these weakly coupled polar-tweed structures leads to a wide spectrum of relaxation times, thus resulting in a dielectric relaxation process, the signature of relaxor ferroelectrics.

Ion-beam-induced bending of semiconductor nanowires.

PubMed

Hanif, Imran; Camara, Osmane; Tunes, Matheus A; Harrison, Robert W; Greaves, Graeme; Donnelly, Stephen E; Hinks, Jonathan A

2018-08-17

The miniaturisation of technology increasingly requires the development of both new structures as well as novel techniques for their manufacture and modification. Semiconductor nanowires (NWs) are a prime example of this and as such have been the subject of intense scientific research for applications ranging from microelectronics to nano-electromechanical devices. Ion irradiation has long been a key processing step for semiconductors and the natural extension of this technique to the modification of semiconductor NWs has led to the discovery of ion beam-induced deformation effects. In this work, transmission electron microscopy with in situ ion bombardment has been used to directly observe the evolution of individual silicon and germanium NWs under irradiation. Silicon NWs were irradiated with either 6 keV neon ions or xenon ions at 5, 7 or 9.5 keV with a flux of 3 × 10 13 ions cm -2 s -1 . Germanium NWs were irradiated with 30 or 70 keV xenon ions with a flux of 10 13 ions cm -2 s -1 . These new results are combined with those reported in the literature in a systematic analysis using a custom implementation of the transport of ions in matter Monte Carlo computer code to facilitate a direct comparison with experimental results taking into account the wide range of experimental conditions. Across the various studies this has revealed underlying trends and forms the basis of a critical review of the various mechanisms which have been proposed to explain the deformation of semiconductor NWs under ion irradiation.

Laser Induced Fluorescence Studies of Electrostatic Double Layers in an Expanding Helicon Plasma

NASA Astrophysics Data System (ADS)

Carr, Jerry, Jr.

We report the first evidence of a laboratory double layer (DL) collapsing in the presence of an instability studied by Chakraborty Thakur et al. 1 with the use of time resolved laser induced fluorescence (LIF) studies. Higher time resolution studies then provided the first statistically validated proof of the correlation between the ion acoustic instability and a DL. Time-frequency analysis in the form of time resolved cross power spectra and continuous wavelet transforms were used to provide insight into beam formation. The implications of this work is that in the creation of strong DLs in expanding plasmas for plasma propulsion or other applications may be self-limited through instability growth. Over the past decade, experimental and theoretical studies have demonstrated the formation of stable, electrostatic, current-free double layers (CFDLs) in plasmas with a strong density gradient; typically a result of a divergent magnetic field. In this work, we present evidence for the formation of multiple double layers within a single divergent magnetic field structure. Downstream of the divergent magnetic field, multiple accelerated ion populations are observed through laser induced fluorescence measurements of the ion velocity distribution function. The formation of the multiple double layer structure is a strong function of the neutral gas pressure in the experiment. The similarity of the accelerated ion populations observed in these laboratory experiments to ion populations observed in reconnection outflow regions in the magnetosphere and in numerical simulations is also described. If ion energization during magnetic reconnection also results solely from acceleration in electric fields, these observations imply a prediction that the ion heating, i.e., the broadening of ion velocity distribution functions, reported in magnetic reconnection experiments is more accurately described by a superposition of differently accelerated ion populations. Therefore, the ion gheatingh rate during reconnection should scale as the square root of the cube of the charge per unit mass (q3/m)1/2 for ions with varying charge-to-mass ratios. A new RFEA probe was benchmarked on the low pressure CFDL plasmas produced in WVU HELIX-LEIA. This work was the result of collaboration between the University of Tromso (UiT) and WVU. LIF was used to confirm the RFEAs ability to detect a beam when one was present. The RFEA was also able to detect the presence of a beam when LIF techniques were limited by metastable quenching. The probefs limitations in dealing with ion focusing are discussed as well.

Ion implantation disorder in strained-layer superlattices

NASA Astrophysics Data System (ADS)

Arnold, G. W.; Picraux, S. T.; Peercy, P. S.; Myers, D. R.; Biefeld, R. M.; Dawson, L. R.

Cantilever beam bending and RBS channeling measurements have been used to examine implantation induced disorder and stress buildup in InO 2GaO 8As/GaAs SLS structures. The critical fluence for saturation of compressive stress occurs prior to amorphous layer formation and is followed by stress relief. For all the ions the maximum ion induced stress scales with energy density into atomic processes and stress relief occurs above approximately 1x10 to the 20th keV/1 cubic cm. Stress relief is more pronounced for the SLSs than for bulk GaAs. Stress relief may lead to slip or other forms of inelastic material flow in SLSs, which would be undesirable for active regions in device applications. Such material flow may be avoided by limiting maximum fluences or by multiple step or simultaneous implantation and annealing for high fluences.

Phosphate barrier on pore-filled cation-exchange membrane for blocking complexing ions in presence of non-complexing ions

NASA Astrophysics Data System (ADS)

Chavan, Vivek; Agarwal, Chhavi; Shinde, Rakesh N.

2018-06-01

In present work, an approach has been used to form a phosphate groups bearing surface barrier on a cation-exchange membrane (CEM). Using optimized conditions, the phosphate bearing monomer bis[2-(methacryloyloxy)ethyl] phosphate has been grafted on the surface of the host poly(ethersulfone) membranes using UV light induced polymerization. The detailed characterizations have shown that less than a micron layer of phosphate barrier is formed without disturbing the original microporous structure of the host membrane. The pores of thus formed membrane have been blocked by cationic-gel formed by in situ UV-initiator induced polymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid along with crosslinker ethylene glycol dimethacrylate in the pores of the membrane. UV-initiator is required for pore-filling as UV light would not penetrate the interior matrix of the membrane. The phosphate functionalized barrier membrane has been examined for permselectivity using a mixture of representative complexing Am3+ ions and non-complexing Cs+ ions. This experiment has demonstrated that complex forming Am3+ ions are blocked by phosphate barrier layer while non-complexing Cs+ ions are allowed to pass through the channels formed by the crosslinked cationic gel.

Bennett ion mass spectrometers on the Pioneer Venus Bus and Orbiter

NASA Technical Reports Server (NTRS)

Taylor, H. A., Jr.; Brinton, H. C.; Wagner, T. C. G.; Blackwell, B. H.; Cordier, G. R.

1980-01-01

Identical Bennett radio-frequency ion mass spectrometer instruments on the Pioneer Venus Bus and Orbiter have provided the first in-situ measurements of the detailed composition of the planet's ionosphere. The sensitivity, resolution, and dynamic range are sufficient to provide measurements of the solar-wind-induced bow-shock, the ionopause, and highly structured distributions of up to 16 thermal ion species within the ionosphere. The use of adaptive scan and detection circuits and servo-controlled logic for ion mass and energy analysis permits detection of ion concentrations as low as 5 ions/cu cm and ion flow velocities as large as 9 km/sec for O(+). A variety of commandable modes provides ion sampling rates ranging from 0.1 to 1.6 sec between measurements of a single constituent. A lightweight sensor and electronics housing are features of a compact instrument package.

Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects.

PubMed

Hack, John; Grills, David C; Miller, John R; Mani, Tomoyasu

2016-02-18

Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.

Cyclotron Phase-Coherent Ion Spatial Dispersion in a Non-Quadratic Trapping Potential is Responsible for FT-ICR MS at the Cyclotron Frequency

NASA Astrophysics Data System (ADS)

Nagornov, Konstantin O.; Kozhinov, Anton N.; Tsybin, Yury O.

2018-01-01

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) at the cyclotron frequency instead of the reduced cyclotron frequency has been experimentally demonstrated using narrow aperture detection electrode (NADEL) ICR cells. Here, based on the results of SIMION simulations, we provide the initial mechanistic insights into the cyclotron frequency regime generation in FT-ICR MS. The reason for cyclotron frequency regime is found to be a new type of a collective motion of ions with a certain dispersion in the initial characteristics, such as pre-excitation ion velocities, in a highly non-quadratic trapping potential as realized in NADEL ICR cells. During ion detection, ions of the same m/z move in phase for cyclotron ion motion but out of phase for magnetron (drift) ion motion destroying signals at the fundamental and high order harmonics that comprise reduced cyclotron frequency components. After an initial magnetron motion period, ion clouds distribute into a novel type of structures - ion slabs, elliptical cylinders, or star-like structures. These structures rotate at the Larmor (half-cyclotron) frequency on a plane orthogonal to the magnetic field, inducing signals at the true cyclotron frequency on each of the narrow aperture detection electrodes. To eliminate the reduced cyclotron frequency peak upon dipolar ion detection, a number of slabs or elliptical cylinders organizing a star-like configuration are formed. In a NADEL ICR cell with quadrupolar ion detection, a single slab or an elliptical cylinder is sufficient to minimize the intensity of the reduced cyclotron frequency components, particularly the second harmonic. [Figure not available: see fulltext.

Electro- and Magneto-Modulated Ion Transport through Graphene Oxide Membranes

PubMed Central

Sun, Pengzhan; Zheng, Feng; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Zhu, Hongwei

2014-01-01

The control of ion trans-membrane transport through graphene oxide (GO) membranes is achieved by electric and magnetic fields. Electric field can either increase or decrease the ion transport through GO membranes depending on its direction, and magnetic field can enhance the ion penetration monotonically. When electric field is applied across GO membrane, excellent control of ion fluidic flows can be done. With the magnetic field, the effective anchoring of ions is demonstrated but the modulation of the ion flowing directions does not occur. The mechanism of the electro- and magneto-modulated ion trans-membrane transport is investigated, indicating that the electric fields dominate the ion migration process while the magnetic fields tune the structure of nanocapillaries within GO membranes. Results also show that the ion selectivity of GO membranes can be tuned with the electric fields while the transport of ions can be enhanced synchronously with the magnetic fields. These excellent properties make GO membranes promising in areas such as field-induced mass transport control and membrane separation. PMID:25347969

Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belianinov, Alex; Burch, Matthew J.; Hysmith, Holland E.

Transitioning to multi-material systems as either interfaced 2D materials or 3D heterostructures can lead to the next generation multi-functional device architectures. Combined direct physical and chemical nanoscale control of these systems offers a new way to tailor material and device functionality as functional structures reach their physical limit. Transition metal thiophosphate (TPS), Cu 1-xIn 1+x/3P 2S 6, that have ferroelectric polarization behavior as layered crystals at room temperature and above make them attractive candidates for direct material sculpting of both chemical and functional properties. The bulk material exhibits stable ferroelectric polarization corroborated by domain structures, rewritable polarization, and hysteresis loops.more » Our previous studies have demonstrated that ferroic order persists on the surface and that spinoidal decomposition of ferroelectric and paraelectric phases occurs in non-stoichiometric Cu/In ratio formulations. Here, we elucidate the chemical changes induced through helium ion irradiation in the TPS family library with varying Cu/In ratio formulations using correlated AFM and ToF-SIMS imaging. We correlate nano- and micro- structures that scale, in area and volume, to the total dose of the helium ion beam, as well as the overall copper concentration in the sample. Furthermore, our ToF-SIMS results show that ion irradiation leads to oxygen penetration as a function of Cu concentration, and proceeds along the Cu domains to the stopping distance of the helium ions in the TPS material. These results opens up new opportunities to understand and implement ferroicly coupled van der Waal devices into an existing framework of 2D heterostructures by locally tuning material chemistry and functionality.« less

Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam

DOE PAGES

Belianinov, Alex; Burch, Matthew J.; Hysmith, Holland E.; ...

2017-11-30

Transitioning to multi-material systems as either interfaced 2D materials or 3D heterostructures can lead to the next generation multi-functional device architectures. Combined direct physical and chemical nanoscale control of these systems offers a new way to tailor material and device functionality as functional structures reach their physical limit. Transition metal thiophosphate (TPS), Cu 1-xIn 1+x/3P 2S 6, that have ferroelectric polarization behavior as layered crystals at room temperature and above make them attractive candidates for direct material sculpting of both chemical and functional properties. The bulk material exhibits stable ferroelectric polarization corroborated by domain structures, rewritable polarization, and hysteresis loops.more » Our previous studies have demonstrated that ferroic order persists on the surface and that spinoidal decomposition of ferroelectric and paraelectric phases occurs in non-stoichiometric Cu/In ratio formulations. Here, we elucidate the chemical changes induced through helium ion irradiation in the TPS family library with varying Cu/In ratio formulations using correlated AFM and ToF-SIMS imaging. We correlate nano- and micro- structures that scale, in area and volume, to the total dose of the helium ion beam, as well as the overall copper concentration in the sample. Furthermore, our ToF-SIMS results show that ion irradiation leads to oxygen penetration as a function of Cu concentration, and proceeds along the Cu domains to the stopping distance of the helium ions in the TPS material. These results opens up new opportunities to understand and implement ferroicly coupled van der Waal devices into an existing framework of 2D heterostructures by locally tuning material chemistry and functionality.« less

Improvement of the magnetic moment of NiZn ferrites induced by substitution of Nd3+ ions for Fe3+ ions

NASA Astrophysics Data System (ADS)

Wu, Xuehang; Chen, Wen; Wu, Wenwei; Wu, Juan; Wang, Qing

2018-05-01

Four types of Ni-Zn based ferrites materials having the general formula Ni0.5Zn0.5NdxFe2-xO4 (0.0 ≤ x ≤ 0.12) have been successfully synthesized by calcining oxalates in air and the influence of Nd content on the structure and magnetic properties of Ni0.5Zn0.5NdxFe2-xO4 is studied. X-ray diffraction examination confirms that a high-crystallized Ni0.5Zn0.5NdxFe2-xO4 with cubic spinel structure is obtained when the precursor is calcined at 1000 °C in air for 2 h. The substitutions of Nd3+ ions for partial Fe3+ ions do not change the spinel crystalline structure of MFe2O4. The incorporation of Nd3+ ions in place of Fe3+ ions in Ni-Zn ferrites increases the average crystallite size. Specific saturation magnetization decreases with increase in Nd content. This is because Nd3+ ions with smaller magnetic moment preferentially fill the octahedral sites. In addition, antiferromagnetic FeNdO3 increases with increase in Nd content. In this study, Ni0.5Zn0.5Nd0.08Fe1.92O4, calcined at 1000 °C, exhibits the highest magnetic moment (4.2954 μB) and the lowest coercivity (28.82 Oe).

Matrix effects in ion-induced emission as observed in Ne collisions with Cu-Mg and Cu-Al alloys

NASA Technical Reports Server (NTRS)

Ferrante, J.; Pepper, S. V.

1983-01-01

Ion induced Auger electron emission is used to study the surfaces of Al, Mg, Cu - 10 at. % Al, Cu - 19.6 at. % Al, and Cu - 7.4 at. % Mg. A neon (Ne) ion beam whose energy is varied from 0.5 to 3 keV is directed at the surface. Excitation of the lighter Ne occurs by the promotion mechanism of Barat and Lichten in asymmetric collisions with Al or Mg atoms. Two principal Auger peaks are observed in the Ne spectrum: one at 22 eV and one at 25 eV. Strong matrix effects are observed in the alloys as a function of energy in which the population of the second peak is greatly enhanced relative to the first over the pure materials. For the pure material over this energy range this ratio is 1.0. For the alloys it can rise to the electronic structure of alloys and to other surface tools such as secondary ion mass spectroscopy.

Radiation-induced segregation and precipitation behaviours around cascade clusters under electron irradiation.

PubMed

Sueishi, Yuichiro; Sakaguchi, Norihito; Shibayama, Tamaki; Kinoshita, Hiroshi; Takahashi, Heishichiro

2003-01-01

We have investigated the formation of cascade clusters and structural changes in them by means of electron irradiation following ion irradiation in an austenitic stainless steel. Almost all of the cascade clusters, which were introduced by the ion irradiation, grew to form interstitial-type dislocation loops or vacancy-type stacking fault tetrahedra after electron irradiation at 623 K, whereas a few of the dot-type clusters remained in the matrix. It was possible to recognize the concentration of Ni and Si by radiation-induced segregation around the dot-type clusters. After electron irradiation at 773 K, we found that some cascade clusters became precipitates (delta-Ni2Si) due to radiation-induced precipitation. This suggests that the cascade clusters could directly become precipitation sites during irradiation.

Phase transformation and microstructural evolution of nanostructured oxides and nitrides under ion irradiations

NASA Astrophysics Data System (ADS)

Lu, Fengyuan

Material design at the nanometer scale is an effective strategy for developing advanced materails with enhanced radiation tolerance for advanced nuclear energy systems as high densities of surfaces and interfaces of the nanostructured materials may behave as effective sinks for defect recovery. However, nanostructured materials may not be intrinsically radiation tolerant, and the interplay among the factors of crystal size, temperature, chemical composition, surface energy and radiation conditions may eventually determine material radiation behaviors. Therefore, it is necessary to understand the radiation effects of nanostructured materials and the underlying physics for the design of advanced nanostructured nuclear materials. The main objective of this doctoral thesis is to study the behavior of nanostructured oxides and nitrides used as fuel matrix and waste forms under extreme radiation conditions with the focus of phase transformation, microstructural evolution and damage mechanisms. Radiation experiments were performed using energetic ion beam techniques to simulate radiation damage resulting from energetic neutrons, alpha-decay events and fission fragments, and various experimental approaches were employed to characterize materials’ microstructural evolution and phase stability upon intense radiation environments including transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. Thermal annealing experiments indicated that nanostructured ZrO2 phase stability is strongly affected by the grain size. Radiation results on nanostructured ZrO2 indicated that thermodynamically unstable or metastable high temperature phases can be induced by energetic beam irradiation at room temperature. Various phase transformation among different polymorphs of monoclinic, tetragonal and amorphous states can be induced, and different mechanisms are responsible for structural transformations including oxygen vacancies accumulation upon displacive damage, radiation-assistant recrystallization and thermal spike by ionization radiation. The radiation response of nanosized pyrochlores indicated that the radiation tolerance of nanoceramics is highly dependent on the composition and size. Nanosized tantalate pyrochlores KxLnyTa2O 7-v (Ln = Gd, Y, Lu) with the average grain size around 10 - 15 nm are highly sensitive to radiation-induced amorphization. The pyrochlore A to B site ionic radius ratio rA/rB is crucial in determining the radiation tolerance of pyrochlores, and a minimum rA/rB of 1.605 exists for the occurring of radiation induced amorphization. The interplay among chemical compositions, structural deviation and grain size eventually determines the phase stability and structural transformation processes of tantalate pyrochlores under intense radiation environments. ZrN shows extremely high phase stability under both displacive ion irradiation and ionizing swift heavy ion irradiation. However, a contraction in lattice constant up to ~ 1.42 % can be induced in nanocrystalline ZrN irradiated with displacive ion beams. In contrast, the strongly ionizing swift heavy ions cannot induce any lattice contraction. Such lattice contractions may be due to a negative strain field in the ZrN nanograins related to N vacancies built up upon displacive radiation. Ion irradiations also lead to the formation of orthorhombic ZrSi phase at the interface between ZrN and Si substrate, resulting from atom mixing and precipitation upon ion irradiations. The fundamental knowledge provides critical data for assessing and quantifying nanostructured ceramics as fuel matrix and waste forms utilized in the extreme environments of advanced nuclear energy systems. Further possibilities are being pursued in manipulating microstructure at the nano-scale, controlling phase stability and tailoring the physical properties of materials for various important engineering applications.

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Anil, E-mail: Anil.Shukla@pnnl.gov; Bogdanov, Bogdan

2015-02-14

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N{sub 2}). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi){sub n}Li{sup +}, (HCOOLi){sub n}Li{sub m}{sup m+}, (HCOOLi){sub n}HCOO{sup −}, and (HCOOLi){sub n}(HCOO){sub m}{sup m−}. Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi){sub 3}Li{sup +} being the most abundant and stable cluster ion. Fragmentations ofmore » singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi){sub 2}) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi){sub 3}Li{sup +} as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.« less

Effect of Ion Streaming on Diffusion of Dust Grains in Dissipative System

NASA Astrophysics Data System (ADS)

Begum, M.; Das, N.

2018-01-01

The presence of strong electric fields in the sheath region of laboratory complex plasma induces an ion drift and perturbs the field around dust grains. The downstream focusing of ions leads to the formation of oscillatory kind of attractive wake potential which superimpose with the normal Debye-Hückel (DH) potential. The structural properties of complex plasma and diffusion coefficient of dust grains in the presence of such a wake potential have been investigated using Langevin dynamics simulation in the subsonic regime of ion flow. The study reveals that the diffusion of dust grains is strongly affected by the ion flow, so that the diffusion changes its character in the wake potential to the DH potential dominant regimes. The dependence of the diffusion coefficient on the parameters, such as the neutral pressure, dust grain size, ion flow velocity, and Coulomb coupling parameter, have been calculated for the subsonic regime by using the Green-Kubo expression, which is based on the integrated velocity autocorrelation function. It is found that the diffusion and the structural property of the system is intimately connected with the interaction potential and significantly get affected in the presence of ion flow in the subsonic regime.

Infrared Spectroscopy of Mobility-Selected H+-Gly-Pro-Gly-Gly (GPGG)

NASA Astrophysics Data System (ADS)

Masson, Antoine; Kamrath, Michael Z.; Perez, Marta A. S.; Glover, Matthew S.; Rothlisberger, U.; Clemmer, David E.; Rizzo, Thomas R.

2015-09-01

We report the first results from a new instrument capable of acquiring infrared spectra of mobility-selected ions. This demonstration involves using ion mobility to first separate the protonated peptide Gly-Pro-Gly-Gly (GPGG) into two conformational families with collisional cross-sections of 93.8 and 96.8 Å2. After separation, each family is independently analyzed by acquiring the infrared predissociation spectrum of the H2-tagged molecules. The ion mobility and spectroscopic data combined with density functional theory (DFT) based molecular dynamics simulations confirm the presence of one major conformer per family, which arises from cis/ trans isomerization about the proline residue. We induce isomerization between the two conformers by using collisional activation in the drift tube and monitor the evolution of the ion distribution with ion mobility and infrared spectroscopy. While the cis-proline species is the preferred gas-phase structure, its relative population is smaller than that of the trans-proline species in the initial ion mobility drift distribution. This suggests that a portion of the trans-proline ion population is kinetically trapped as a higher energy conformer and may retain structural elements from solution.

Modeling Diffusion Induced Stresses for Lithium-Ion Battery Materials

NASA Astrophysics Data System (ADS)

Chiu Huang, Cheng-Kai

Advancing lithium-ion battery technology is of paramount importance for satisfying the energy storage needs in the U.S., especially for the application in the electric vehicle industry. To provide a better acceleration for electric vehicles, a fast and repeatable discharging rate is required. However, particle fractures and capacity loss have been reported under high current rate (C-rate) during charging/discharging and after a period of cycling. During charging and discharging, lithium ions extract from and intercalate into electrode materials accompanied with the volume change and phase transition between Li-rich phase and Li-poor phase. It is suggested that the diffusion-induced-stress is one of the main reasons causing capacity loss due to the mechanical degradation of electrode particles. Therefore, there is a fundamental need to provide a mechanistic understanding by considering the structure-mechanics-property interactions in lithium-ion battery materials. Among many cathode materials, the olivine-based lithium-iron-phosphate (LiFePO4) with an orthorhombic crystal structure is one of the promising cathode materials for the application in electric vehicles. In this research we first use a multiphysic approach to investigate the stress evolution, especially on the phase boundary during lithiation in single LiFePO4 particles. A diffusion-controlled finite element model accompanied with the experimentally observed phase boundary propagation is developed via a finite element package, ANSYS, in which lithium ion concentration-dependent anisotropic material properties and volume misfits are incorporated. The stress components on the phase boundary are used to explain the Mode I, Mode II, and Mode III fracture propensities in LiFePO4 particles. The elastic strain energy evolution is also discussed to explain why a layer-by-layer lithium insertion mechanism (i.e. first-order phase transformation) is energetically preferred. Another importation issue is how current rate (C-rate) during charging/discharging affects diffusion induced stresses inside electrode materials. For the experimental part we first conduct charging/discharging under different C-rates to observe the voltage responses for commercial LiFePO4 batteries. Then Time-of-Flight Secondary Ion Mass Spectrometry technique is applied to measure the lithium ion intensities in different C-rate charged/discharged samples. These experimental results could be used to support that a more significant voltage fluctuation under high C-rates is due to different lithium insertion mechanisms, rather than the amount of lithium ions intercalated into electrode materials. Thus the investigation of C-rate-dependent stress evolution is required for the development of a more durable lithium ion battery. In this dissertation, we extend the single particle finite element model to investigate the C-rate-dependent diffusion induced stresses in a multi-particle system. Concentration dependent anisotropic material properties, C-rate-dependent volume misfits and concentration dependent Li-ion diffusivity are incorporated in the model. The concentration gradients, diffusion induced stresses, and strain energies under different C-rates are discussed in this study. Particle fractures have been observed in many experimental results, in this study we further discuss the effect of the crack surface orientation on the lithium concentration profile and stress level in cathode materials. The results of this dissertation provide a better understanding of diffusion induced stresses in electrode materials and contribute to our fundamental knowledge of interplay between lithium intercalations, stress evolutions, particle fractures and the capacity fade in lithium-ion batteries.

Metallurgical effects on chloride ion corrosion threshold of steel in concrete.

DOT National Transportation Integrated Search

2001-11-30

The chloride-induced corrosion of reinforcing steel bars (rebar) in concrete seriously limits durability of reinforcing concrete structures. This investigation examines key issues in pitting corrosion and chloride corrosion threshold of rebar in alka...

Felling of individual freestanding nanoobjects using focused-ion-beam milling for investigations of structural and transport properties.

PubMed

Li, Wuxia; Fenton, J C; Cui, Ajuan; Wang, Huan; Wang, Yiqian; Gu, Changzhi; McComb, D W; Warburton, P A

2012-03-16

We report that, to enable studies of their compositional, structural and electrical properties, freestanding individual nanoobjects can be selectively felled in a controllable way by the technique of low-current focused-ion-beam (FIB) milling with the ion beam at a chosen angle of incidence to the nanoobject. To demonstrate the suitability of the technique, we report results for zigzag/straight tungsten nanowires grown vertically on support substrates and then felled for characterization. We also describe a systematic investigation of the effect of the experimental geometry and parameters on the felling process and on the induced wire-bending phenomenon. The method of felling freestanding nanoobjects using FIB is an advantageous new technique enabling investigations of the properties of selected individual nanoobjects.

Felling of individual freestanding nanoobjects using focused-ion-beam milling for investigations of structural and transport properties

NASA Astrophysics Data System (ADS)

Li, Wuxia; Fenton, J. C.; Cui, Ajuan; Wang, Huan; Wang, Yiqian; Gu, Changzhi; McComb, D. W.; Warburton, P. A.

2012-03-01

We report that, to enable studies of their compositional, structural and electrical properties, freestanding individual nanoobjects can be selectively felled in a controllable way by the technique of low-current focused-ion-beam (FIB) milling with the ion beam at a chosen angle of incidence to the nanoobject. To demonstrate the suitability of the technique, we report results for zigzag/straight tungsten nanowires grown vertically on support substrates and then felled for characterization. We also describe a systematic investigation of the effect of the experimental geometry and parameters on the felling process and on the induced wire-bending phenomenon. The method of felling freestanding nanoobjects using FIB is an advantageous new technique enabling investigations of the properties of selected individual nanoobjects.

In-situ luminescence monitoring of ion-induced damage evolution in SiO 2 and Al 2O 3

DOE PAGES

Crespillo, Miguel L.; Graham, Joseph T.; Zhang, Yanwen; ...

2015-12-17

Real-time, in-situ ionoluminescence measurements provide information of evolution of emission bands with ion fluence, and thereby establish a correlation between point defect kinetics and phase stability. Using fast light ions (2 MeV H and 3.5 He MeV) and medium mass-high energy ions (8 MeV O, E=0.5 MeV/amu), scintillation materials of a-SiO 2, crystalline quartz, and Al 2O 3 are comparatively investigated at room temperature with the aim of obtaining a further insight on the structural defects induced by ion irradiation and understand the role of electronic energy loss on the damage processes. For more energetic heavy ions, the electronic energymore » deposition pattern offers higher rates of excitation deeper into the material and allows to evaluate the competing mechanisms between the radiative and non-radiative de-excitation processes. Irradiations with 8 MeV O ions have been selected corresponding to the electronic stopping regime, where the electronic stopping power is dominant, and above the critical amorphization threshold for quartz. Lastly, the usefulness of IBIL and its specific capabilities as a sensitive tool to investigate the material characterization and evaluation of radiation effects are demonstrated.« less

X-ray structure of acid-sensing ion channel 1-snake toxin complex reveals open state of a Na(+)-selective channel.

PubMed

Baconguis, Isabelle; Bohlen, Christopher J; Goehring, April; Julius, David; Gouaux, Eric

2014-02-13

Acid-sensing ion channels (ASICs) detect extracellular protons produced during inflammation or ischemic injury and belong to the superfamily of degenerin/epithelial sodium channels. Here, we determine the cocrystal structure of chicken ASIC1a with MitTx, a pain-inducing toxin from the Texas coral snake, to define the structure of the open state of ASIC1a. In the MitTx-bound open state and in the previously determined low-pH desensitized state, TM2 is a discontinuous α helix in which the Gly-Ala-Ser selectivity filter adopts an extended, belt-like conformation, swapping the cytoplasmic one-third of TM2 with an adjacent subunit. Gly 443 residues of the selectivity filter provide a ring of three carbonyl oxygen atoms with a radius of ∼3.6 Å, presenting an energetic barrier for hydrated ions. The ASIC1a-MitTx complex illuminates the mechanism of MitTx action, defines the structure of the selectivity filter of voltage-independent, sodium-selective ion channels, and captures the open state of an ASIC. Copyright © 2014 Elsevier Inc. All rights reserved.

Concentration-dependent and configuration-dependent interactions of monovalent ions with an RNA tetraloop

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miner, Jacob Carlson; Garcia, Angel Enrique

Monovalent salt solutions have strongly coupled interactions with biopolymers, from large polyelectrolytes to small RNA oligomers. High salt concentrations have been known to induce transitions in the structure of RNA, producing non-canonical configurations and even driving RNA to precipitate out of solution. Using all-atom molecular dynamics simulations, we model a monovalent salt species (KCL) at high concentrations (0.1–3m) and calculate the equilibrium distributions of water and ions around a small tetraloop-forming RNA oligomer in a variety of structural arrangements: folded A-RNA (canonical) and Z-RNA (non-canonical) tetraloops and unfolded configurations. From these data, we calculate the ion preferential binding coefficients andmore » Donnan coefficients for the RNA oligomer as a function of concentration and structure. We find that cation accumulation is highest around non-canonical Z-RNA configurations at concentrations below 0.5m, while unfolded configurations accumulate the most co-ions in all concentrations. By contrast, canonical A-RNA structures consistently show the lowest accumulations for all ion species. Water distributions vary markedly with RNA configuration but show little dependency on KCL concentration. Based on Donnan coefficient calculations, the net charge of the solution at the surface of the RNA decreases linearly as a function of salt concentration and becomes net-neutral near 2.5–3m KCL for folded configurations, while unfolded configurations still show a positive solution charge. Our findings show that all-atom molecular dynamics can describe the equilibrium distributions of monovalent salt in the presence of small RNA oligomers at KCL concentrations where ion correlation effects become important. Furthermore, these results provide valuable insights into the distributions of water and ions near the RNA oligomer surface as a function of structural configuration.« less

Concentration-dependent and configuration-dependent interactions of monovalent ions with an RNA tetraloop

DOE PAGES

Miner, Jacob Carlson; Garcia, Angel Enrique

2018-05-29

Monovalent salt solutions have strongly coupled interactions with biopolymers, from large polyelectrolytes to small RNA oligomers. High salt concentrations have been known to induce transitions in the structure of RNA, producing non-canonical configurations and even driving RNA to precipitate out of solution. Using all-atom molecular dynamics simulations, we model a monovalent salt species (KCL) at high concentrations (0.1–3m) and calculate the equilibrium distributions of water and ions around a small tetraloop-forming RNA oligomer in a variety of structural arrangements: folded A-RNA (canonical) and Z-RNA (non-canonical) tetraloops and unfolded configurations. From these data, we calculate the ion preferential binding coefficients andmore » Donnan coefficients for the RNA oligomer as a function of concentration and structure. We find that cation accumulation is highest around non-canonical Z-RNA configurations at concentrations below 0.5m, while unfolded configurations accumulate the most co-ions in all concentrations. By contrast, canonical A-RNA structures consistently show the lowest accumulations for all ion species. Water distributions vary markedly with RNA configuration but show little dependency on KCL concentration. Based on Donnan coefficient calculations, the net charge of the solution at the surface of the RNA decreases linearly as a function of salt concentration and becomes net-neutral near 2.5–3m KCL for folded configurations, while unfolded configurations still show a positive solution charge. Our findings show that all-atom molecular dynamics can describe the equilibrium distributions of monovalent salt in the presence of small RNA oligomers at KCL concentrations where ion correlation effects become important. Furthermore, these results provide valuable insights into the distributions of water and ions near the RNA oligomer surface as a function of structural configuration.« less

Concentration-dependent and configuration-dependent interactions of monovalent ions with an RNA tetraloop

NASA Astrophysics Data System (ADS)

Miner, Jacob Carlson; García, Angel Enrique

2018-06-01

Monovalent salt solutions have strongly coupled interactions with biopolymers, from large polyelectrolytes to small RNA oligomers. High salt concentrations have been known to induce transitions in the structure of RNA, producing non-canonical configurations and even driving RNA to precipitate out of solution. Using all-atom molecular dynamics simulations, we model a monovalent salt species (KCL) at high concentrations (0.1-3m) and calculate the equilibrium distributions of water and ions around a small tetraloop-forming RNA oligomer in a variety of structural arrangements: folded A-RNA (canonical) and Z-RNA (non-canonical) tetraloops and unfolded configurations. From these data, we calculate the ion preferential binding coefficients and Donnan coefficients for the RNA oligomer as a function of concentration and structure. We find that cation accumulation is highest around non-canonical Z-RNA configurations at concentrations below 0.5m, while unfolded configurations accumulate the most co-ions in all concentrations. By contrast, canonical A-RNA structures consistently show the lowest accumulations for all ion species. Water distributions vary markedly with RNA configuration but show little dependency on KCL concentration. Based on Donnan coefficient calculations, the net charge of the solution at the surface of the RNA decreases linearly as a function of salt concentration and becomes net-neutral near 2.5-3m KCL for folded configurations, while unfolded configurations still show a positive solution charge. Our findings show that all-atom molecular dynamics can describe the equilibrium distributions of monovalent salt in the presence of small RNA oligomers at KCL concentrations where ion correlation effects become important. Furthermore, these results provide valuable insights into the distributions of water and ions near the RNA oligomer surface as a function of structural configuration.

Concentration-dependent and configuration-dependent interactions of monovalent ions with an RNA tetraloop.

PubMed

Miner, Jacob Carlson; García, Angel Enrique

2018-06-14

Monovalent salt solutions have strongly coupled interactions with biopolymers, from large polyelectrolytes to small RNA oligomers. High salt concentrations have been known to induce transitions in the structure of RNA, producing non-canonical configurations and even driving RNA to precipitate out of solution. Using all-atom molecular dynamics simulations, we model a monovalent salt species (KCL) at high concentrations (0.1-3m) and calculate the equilibrium distributions of water and ions around a small tetraloop-forming RNA oligomer in a variety of structural arrangements: folded A-RNA (canonical) and Z-RNA (non-canonical) tetraloops and unfolded configurations. From these data, we calculate the ion preferential binding coefficients and Donnan coefficients for the RNA oligomer as a function of concentration and structure. We find that cation accumulation is highest around non-canonical Z-RNA configurations at concentrations below 0.5m, while unfolded configurations accumulate the most co-ions in all concentrations. By contrast, canonical A-RNA structures consistently show the lowest accumulations for all ion species. Water distributions vary markedly with RNA configuration but show little dependency on KCL concentration. Based on Donnan coefficient calculations, the net charge of the solution at the surface of the RNA decreases linearly as a function of salt concentration and becomes net-neutral near 2.5-3m KCL for folded configurations, while unfolded configurations still show a positive solution charge. Our findings show that all-atom molecular dynamics can describe the equilibrium distributions of monovalent salt in the presence of small RNA oligomers at KCL concentrations where ion correlation effects become important. Furthermore, these results provide valuable insights into the distributions of water and ions near the RNA oligomer surface as a function of structural configuration.

Interplay between magnetic order at Mn and Tm sites alongside the structural distortion in multiferroic films of o -TmMn O3

NASA Astrophysics Data System (ADS)

Windsor, Y. W.; Ramakrishnan, M.; Rettig, L.; Alberca, A.; Bothschafter, E. M.; Staub, U.; Shimamoto, K.; Hu, Y.; Lippert, T.; Schneider, C. W.

2015-06-01

We employ resonant soft x-ray diffraction to individually study the magnetic ordering of the Mn and the Tm sublattices in single-crystalline films of orthorhombic (o -) TmMn O3 . The same magnetic ordering wave vector of (0 q 0 ) with q ≈0.46 is found for both ionic species, suggesting that the familiar antiferromagnetic order of the Mn ions induces a magnetic order on the Tm unpaired 4 f electrons. Indeed, intensity variations of magnetic reflections with temperature corroborate this scenario. Calculated magnetic fields at the Tm sites are used as a model magnetic structure for the Tm, which correctly predicts intensity variations at the Tm resonance upon azimuthal rotation of the sample. The model allows ruling out a b c -cycloid modulation of the Mn ions as the cause for the incommensurate ordering, as found in TbMn O3 . The structural distortion, which occurs in the ferroelectric phase below TC, was followed through nonresonant diffraction of structural reflections forbidden by the high-temperature crystal symmetry. The (0 q 0 ) magnetic reflection appears at the Mn resonance well above TC, indicating that this reflection is sensitive also to the intermediate sinusoidal magnetic phase. The model presented suggests that the Tm 4 f electrons are polarized well above the ferroelectric transition and are possibly not affected by the transition at TC. The successful description of the induced order observed at the Tm resonance is a promising example for future element-selective studies in which "spectator" ions may allow access to previously unobtainable information about other constituent ions.

Selectivity of externally facing ion-binding sites in the Na/K pump to alkali metals and organic cations

PubMed Central

Ratheal, Ian M.; Virgin, Gail K.; Yu, Haibo; Roux, Benoît; Gatto, Craig; Artigas, Pablo

2010-01-01

The Na/K pump is a P-type ATPase that exchanges three intracellular Na+ ions for two extracellular K+ ions through the plasmalemma of nearly all animal cells. The mechanisms involved in cation selection by the pump's ion-binding sites (site I and site II bind either Na+ or K+; site III binds only Na+) are poorly understood. We studied cation selectivity by outward-facing sites (high K+ affinity) of Na/K pumps expressed in Xenopus oocytes, under voltage clamp. Guanidinium+, methylguanidinium+, and aminoguanidinium+ produced two phenomena possibly reflecting actions at site III: (i) voltage-dependent inhibition (VDI) of outwardly directed pump current at saturating K+, and (ii) induction of pump-mediated, guanidinium-derivative–carried inward current at negative potentials without Na+ and K+. In contrast, formamidinium+ and acetamidinium+ induced K+-like outward currents. Measurement of ouabain-sensitive ATPase activity and radiolabeled cation uptake confirmed that these cations are external K+ congeners. Molecular dynamics simulations indicate that bound organic cations induce minor distortion of the binding sites. Among tested metals, only Li+ induced Na+-like VDI, whereas all metals tested except Na+ induced K+-like outward currents. Pump-mediated K+-like organic cation transport challenges the concept of rigid structural models in which ion specificity at site I and site II arises from a precise and unique arrangement of coordinating ligands. Furthermore, actions by guanidinium+ derivatives suggest that Na+ binds to site III in a hydrated form and that the inward current observed without external Na+ and K+ represents cation transport when normal occlusion at sites I and II is impaired. These results provide insights on external ion selectivity at the three binding sites. PMID:20937860

Energetic-ion-driven global instabilities in stellarator/helical plasmas and comparison with tokamak plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Toi, K.; Ogawa, K.; Isobe, M.

2011-01-01

Comprehensive understanding of energetic-ion-driven global instabilities such as Alfven eigenmodes (AEs) and their impact on energetic ions and bulk plasma is crucially important for tokamak and stellarator/helical plasmas and in the future for deuterium-tritium (DT) burning plasma experiments. Various types of global modes and their associated enhanced energetic ion transport are commonly observed in toroidal plasmas. Toroidicity-induced AEs and ellipticity-induced AEs, whose gaps are generated through poloidal mode coupling, are observed in both tokamak and stellarator/helical plasmas. Global AEs and reversed shear AEs, where toroidal couplings are not as dominant were also observed in those plasmas. Helicity induced AEs thatmore » exist only in 3D plasmas are observed in the large helical device (LHD) and Wendelstein 7 Advanced Stellarator plasmas. In addition, the geodesic acoustic mode that comes from plasma compressibility is destabilized by energetic ions in both tokamak and LHD plasmas. Nonlinear interaction of these modes and their influence on the confinement of the bulk plasma as well as energetic ions are observed in both plasmas. In this paper, the similarities and differences in these instabilities and their consequences for tokamak and stellarator/helical plasmas are summarized through comparison with the data sets obtained in LHD. In particular, this paper focuses on the differences caused by the rotational transform profile and the 2D or 3D geometrical structure of the plasma equilibrium. Important issues left for future study are listed.« less

Dose--response of initial G2-chromatid breaks induced in normal human fibroblasts by heavy ions

NASA Technical Reports Server (NTRS)

Kawata, T.; Durante, M.; Furusawa, Y.; George, K.; Takai, N.; Wu, H.; Cucinotta, F. A.; Dicello, J. F. (Principal Investigator)

2001-01-01

PURPOSE: To investigate initial chromatid breaks in prematurely condensed G2 chromosomes following exposure to heavy ions of different LET. MATERIAL AND METHODS: Exponentially growing human fibroblast cells AG1522 were irradiated with gamma-rays, energetic carbon (13 keV/ microm, 80 keV/microm), silicon (55 keV/microm) and iron (140 keV/microm, 185keV/microm, 440keV/microm) ions. Chromosomes were prematurely condensed using calyculin-A. Initial chromatid-type and isochromatid breaks in G2 cells were scored. RESULTS: The dose response curves for total chromatid breaks were linear regardless of radiation type. The relative biological effectiveness (RBE) showed a LET-dependent increase, peaking around 2.7 at 55-80keV/microm and decreasing at higher LET. The dose response curves for isochromatid-type breaks were linear for high-LET radiations, but linear-quadratic for gamma-rays and 13 keV/microm carbon ions. The RBE for the induction of isochromatid breaks obtained from linear components increased rapidly between 13keV/microm (about 7) and 80keV/microm carbon (about 71), and decreased gradually until 440 keV/microm iron ions (about 66). CONCLUSIONS: High-LET radiations are more effective at inducing isochromatid breaks, while low-LET radiations are more effective at inducing chromatid-type breaks. The densely ionizing track structures of heavy ions and the proximity of sister chromatids in G2 cells result in an increase in isochromatid breaks.

Nanoscale volcanoes: accretion of matter at ion-sculpted nanopores.

PubMed

Mitsui, Toshiyuki; Stein, Derek; Kim, Young-Rok; Hoogerheide, David; Golovchenko, J A

2006-01-27

We demonstrate the formation of nanoscale volcano-like structures induced by ion-beam irradiation of nanoscale pores in freestanding silicon nitride membranes. Accreted matter is delivered to the volcanoes from micrometer distances along the surface. Volcano formation accompanies nanopore shrinking and depends on geometrical factors and the presence of a conducting layer on the membrane's back surface. We argue that surface electric fields play an important role in accounting for the experimental observations.

Structures and physical properties of gaseous metal cationized biological ions.

PubMed

Burt, Michael B; Fridgen, Travis D

2012-01-01

Metal chelation can alter the activity of free biomolecules by modifying their structures or stabilizing higher energy tautomers. In recent years, mass spectrometric techniques have been used to investigate the effects of metal complexation with proteins, nucleobases and nucleotides, where small conformational changes can have significant physiological consequences. In particular, infrared multiple photon dissociation spectroscopy has emerged as an important tool for determining the structure and reactivity of gas-phase ions. Unlike other mass spectrometric approaches, this method is able to directly resolve structural isomers using characteristic vibrational signatures. Other activation and dissociation methods, such as blackbody infrared radiative dissociation or collision-induced dissociation can also reveal information about the thermochemistry and dissociative pathways of these biological ions. This information can then be used to provide information about the structures of the ionic complexes under study. In this article, we review the use of gas-phase techniques in characterizing metal-bound biomolecules. Particular attention will be given to our own contributions, which detail the ability of metal cations to disrupt nucleobase pairs, direct the self-assembly of nucleobase clusters and stabilize non-canonical isomers of amino acids.

Differentiation of the Stereochemistry and Anomeric Configuration for 1-3 Linked Disaccharides Via Tandem Mass Spectrometry and 18O-labeling

NASA Astrophysics Data System (ADS)

Konda, Chiharu; Bendiak, Brad; Xia, Yu

2012-02-01

Collision-induced dissociation (CID) of deprotonated hexose-containing disaccharides ( m/z 341) with 1-2, 1-4, and 1-6 linkages yields product ions at m/z 221, which have been identified as glycosyl-glycolaldehyde anions. From disaccharides with these linkages, CID of m/z 221 ions produces distinct fragmentation patterns that enable the stereochemistries and anomeric configurations of the non-reducing sugar units to be determined. However, only trace quantities of m/z 221 ions can be generated for 1-3 linkages in Paul or linear ion traps, preventing further CID analysis. Here we demonstrate that high intensities of m/z 221 ions can be built up in the linear ion trap (Q3) from beam-type CID of a series of 1-3 linked disaccharides conducted on a triple quadrupole/linear ion trap mass spectrometer. 18O-labeling at the carbonyl position of the reducing sugar allowed mass-discrimination of the "sidedness" of dissociation events to either side of the glycosidic linkage. Under relatively low energy beam-type CID and ion trap CID, an m/z 223 product ion containing 18O predominated. It was a structural isomer that fragmented quite differently than the glycosyl-glycolaldehydes and did not provide structural information about the non-reducing sugar. Under higher collision energy beam-type CID conditions, the formation of m/z 221 ions, which have the glycosyl-glycolaldehyde structures, were favored. Characteristic fragmentation patterns were observed for each m/z 221 ion from higher energy beam-type CID of 1-3 linked disaccharides and the stereochemistry of the non-reducing sugar, together with the anomeric configuration, were successfully identified both with and without 18O-labeling of the reducing sugar carbonyl group.

Effects of Fe concentration on the ion-irradiation induced defect evolution and hardening in Ni-Fe solid solution alloys

DOE PAGES

Jin, Ke; Guo, Wei; Lu, Chenyang; ...

2016-12-01

Understanding alloying effects on the irradiation response of structural materials is pivotal in nuclear engineering. In order to systematically explore the effects of Fe concentration on the irradiation-induced defect evolution and hardening in face-centered cubic Ni-Fe binary solid solution alloys, single crystalline Ni-xFe (x = 0–60 at%) alloys have been grown and irradiated with 1.5 MeV Ni ions. The irradiations have been performed over a wide range of fluences from 3 × 10 13 to 3 × 10 16 cm -2 at room temperature. Ion channeling technique has shown reduced damage accumulation with increasing Fe concentration in the low fluencemore » regime, which is consistent to the results from molecular dynamic simulations. We did not observe any irradiation-induced compositional segregation in atom probe tomography within the detection limit, even in the samples irradiated with high fluence Ni ions. Transmission electron microscopy analyses have further demonstrated that the defect size significantly decreases with increasing Fe concentration, indicating a delay in defect evolution. Furthermore, irradiation induced hardening has been measured by nanoindentation tests. Ni and the Ni-Fe alloys have largely different initial hardness, but they all follow a similar trend for the increase of hardness as a function of irradiation fluence.« less

Effects of Fe concentration on the ion-irradiation induced defect evolution and hardening in Ni-Fe solid solution alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Ke; Guo, Wei; Lu, Chenyang

Understanding alloying effects on the irradiation response of structural materials is pivotal in nuclear engineering. In order to systematically explore the effects of Fe concentration on the irradiation-induced defect evolution and hardening in face-centered cubic Ni-Fe binary solid solution alloys, single crystalline Ni-xFe (x = 0–60 at%) alloys have been grown and irradiated with 1.5 MeV Ni ions. The irradiations have been performed over a wide range of fluences from 3 × 10 13 to 3 × 10 16 cm -2 at room temperature. Ion channeling technique has shown reduced damage accumulation with increasing Fe concentration in the low fluencemore » regime, which is consistent to the results from molecular dynamic simulations. We did not observe any irradiation-induced compositional segregation in atom probe tomography within the detection limit, even in the samples irradiated with high fluence Ni ions. Transmission electron microscopy analyses have further demonstrated that the defect size significantly decreases with increasing Fe concentration, indicating a delay in defect evolution. Furthermore, irradiation induced hardening has been measured by nanoindentation tests. Ni and the Ni-Fe alloys have largely different initial hardness, but they all follow a similar trend for the increase of hardness as a function of irradiation fluence.« less

Online in situ x-ray diffraction setup for structural modification studies during swift heavy ion irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grygiel, C.; Lebius, H.; Bouffard, S.

2012-01-15

The high energy density of electronic excitations due to the impact of swift heavy ions can induce structural modifications in materials. We present an x-ray diffractometer called ALIX (''Analyse en Ligne sur IRRSUD par diffraction de rayons X''), which has been set up at the low-energy beamline (IRRadiation SUD - IRRSUD) of the Grand Accelerateur National d'Ions Lourds facility, to allow the study of structural modification kinetics as a function of the ion fluence. The x-ray setup has been modified and optimized to enable irradiation by swift heavy ions simultaneously to x-ray pattern recording. We present the capability of ALIXmore » to perform simultaneous irradiation-diffraction by using energy discrimination between x-rays from diffraction and from ion-target interaction. To illustrate its potential, results of sequential or simultaneous irradiation-diffraction are presented in this article to show radiation effects on the structural properties of ceramics. Phase transition kinetics have been studied during xenon ion irradiation of polycrystalline MgO and SrTiO{sub 3}. We have observed that MgO oxide is radiation-resistant to high electronic excitations, contrary to the high sensitivity of SrTiO{sub 3}, which exhibits transition from the crystalline to the amorphous state during irradiation. By interpreting the amorphization kinetics of SrTiO{sub 3}, defect overlapping models are discussed as well as latent track characteristics. Together with a transmission electron microscopy study, we conclude that a single impact model describes the phase transition mechanism.« less

Application of pulsed multi-ion irradiations in radiation damage research: A stochastic cluster dynamics simulation study

NASA Astrophysics Data System (ADS)

Hoang, Tuan L.; Nazarov, Roman; Kang, Changwoo; Fan, Jiangyuan

2018-07-01

Under the multi-ion irradiation conditions present in accelerated material-testing facilities or fission/fusion nuclear reactors, the combined effects of atomic displacements with radiation products may induce complex synergies in the structural materials. However, limited access to multi-ion irradiation facilities and the lack of computational models capable of simulating the evolution of complex defects and their synergies make it difficult to understand the actual physical processes taking place in the materials under these extreme conditions. In this paper, we propose the application of pulsed single/dual-beam irradiation as replacements for the expensive steady triple-beam irradiation to study radiation damages in materials under multi-ion irradiation.

Fabrication of ion bombardment induced rippled TiO₂ surfaces to influence subsequent organic thin film growth.

PubMed

Kratzer, Markus; Szajna, Konrad; Wrana, Domink; Belza, Wojciech; Krok, Franciszek; Teichert, Christian

2018-05-23

Control over organic thin film growth is a central issue in the development of organic electronics. The anisotropy and extended size of the molecular building blocks introduce a high degree of complexity within the formation of thin films. This complexity can be even increased for substrates with induced, sophisticated morphology and anisotropy. Thus, targeted structuring like ion beam mediated modification of substrates in order to create ripples, pyramids, or pit structures provides a further degree of freedom in manipulating the growth morphology of organic thin films. We provide a comprehensive review of recent work on para-hexaphenyl (C36H26, 6P) as a typical representative of the class of small, rod-like conjugated molecules and rutile TiO2(110) as an example for a transparent oxide electrode to demonstrate the effect of ion beam induced nanostructuring on organic thin film growth. Starting from molecular growth on smooth, atomically flat TiO2(110) (11) surfaces, we investigate the influence of the ripple size on the resulting 6P thin films. The achieved 6P morphologies are either crystalline nano-needles composed of flat lying molecules or islands consisting of upright standing 6P, which are elongated in ripple direction. The islands' length to width ratio can be controlled by tuning of the ripples' shape. © 2018 IOP Publishing Ltd.

Mini ion trap mass spectrometer

DOEpatents

Dietrich, Daniel D.; Keville, Robert F.

1995-01-01

An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

Mini ion trap mass spectrometer

DOEpatents

Dietrich, D.D.; Keville, R.F.

1995-09-19

An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

Electron source for a mini ion trap mass spectrometer

DOEpatents

Dietrich, Daniel D.; Keville, Robert F.

1995-01-01

An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

Photoionization and ion cyclotron resonance studies of the ion chemistry of ethylene oxide

NASA Technical Reports Server (NTRS)

Corderman, R. R.; Williamson, A. D.; Lebreton, P. R.; Buttrill, S. E., Jr.; Beauchamp, J. L.

1976-01-01

The formation of the ethylene oxide molecular ion and its subsequent ion-molecule reactions leading to the products C2H5O(+) and C3H5O(+) have been studied using time-resolved photoionization mass spectroscopy, ion cyclotron resonance spectroscopy, and photoelectron spectroscopy. An examination of the effects of internal energy on reactivity shows that the ratio of C3H5O(+) to C2H5O(+) increases by an order of magnitude with a single quantum of vibrational energy. The formation of (C2H4O/+/)-asterisk in a collision-induced isomerization is found which yields a ring-opened structure by C-C bond cleavage. The relaxed ring-opened C2H4O(+) ion reacts with neutral ethylene oxide by CH2(+) transfer to yield an intermediate product ion C3H6O(+) which gives C3H5O(+) by loss of H.

Identification of ion-channel modulators that protect against aminoglycoside-induced hair cell death

PubMed Central

Kenyon, Emma J.; Kirkwood, Nerissa K.; Kitcher, Siân R.; O’Reilly, Molly; Cantillon, Daire M.; Goodyear, Richard J.; Secker, Abigail; Baxendale, Sarah; Bull, James C.; Waddell, Simon J.; Whitfield, Tanya T.; Ward, Simon E.; Kros, Corné J.; Richardson, Guy P.

2017-01-01

Aminoglycoside antibiotics are used to treat life-threatening bacterial infections but can cause deafness due to hair cell death in the inner ear. Compounds have been described that protect zebrafish lateral line hair cells from aminoglycosides, but few are effective in the cochlea. As the aminoglycosides interact with several ion channels, including the mechanoelectrical transducer (MET) channels by which they can enter hair cells, we screened 160 ion-channel modulators, seeking compounds that protect cochlear outer hair cells (OHCs) from aminoglycoside-induced death in vitro. Using zebrafish, 72 compounds were identified that either reduced loading of the MET-channel blocker FM 1-43FX, decreased Texas red–conjugated neomycin labeling, or reduced neomycin-induced hair cell death. After testing these 72 compounds, and 6 structurally similar compounds that failed in zebrafish, 13 were found that protected against gentamicin-induced death of OHCs in mouse cochlear cultures, 6 of which are permeant blockers of the hair cell MET channel. None of these compounds abrogated aminoglycoside antibacterial efficacy. By selecting those without adverse effects at high concentrations, 5 emerged as leads for developing pharmaceutical otoprotectants to alleviate an increasing clinical problem. PMID:29263311

Identification of ion-channel modulators that protect against aminoglycoside-induced hair cell death.

PubMed

Kenyon, Emma J; Kirkwood, Nerissa K; Kitcher, Siân R; O'Reilly, Molly; Derudas, Marco; Cantillon, Daire M; Goodyear, Richard J; Secker, Abigail; Baxendale, Sarah; Bull, James C; Waddell, Simon J; Whitfield, Tanya T; Ward, Simon E; Kros, Corné J; Richardson, Guy P

2017-12-21

Aminoglycoside antibiotics are used to treat life-threatening bacterial infections but can cause deafness due to hair cell death in the inner ear. Compounds have been described that protect zebrafish lateral line hair cells from aminoglycosides, but few are effective in the cochlea. As the aminoglycosides interact with several ion channels, including the mechanoelectrical transducer (MET) channels by which they can enter hair cells, we screened 160 ion-channel modulators, seeking compounds that protect cochlear outer hair cells (OHCs) from aminoglycoside-induced death in vitro. Using zebrafish, 72 compounds were identified that either reduced loading of the MET-channel blocker FM 1-43FX, decreased Texas red-conjugated neomycin labeling, or reduced neomycin-induced hair cell death. After testing these 72 compounds, and 6 structurally similar compounds that failed in zebrafish, 13 were found that protected against gentamicin-induced death of OHCs in mouse cochlear cultures, 6 of which are permeant blockers of the hair cell MET channel. None of these compounds abrogated aminoglycoside antibacterial efficacy. By selecting those without adverse effects at high concentrations, 5 emerged as leads for developing pharmaceutical otoprotectants to alleviate an increasing clinical problem.

Variations of water's local-structure induced by solvation of NaCl

NASA Astrophysics Data System (ADS)

Gu, Bin; Zhang, Feng-Shou; Huang, Yu-Gai; Fang, Xia

2010-03-01

The researches on the structure of water and its changes induced by solutes are of enduring interests. The changes of the local structure of liquid water induced by NaCl solute under ambient conditions are studied and presented quantitatively with some order parameters and visualized with 2-body and 3-body correlation functions. The results show that, after the NaCl are solvated, the translational order t of water is decreased for the suppression of the second hydration shells around H2O molecules; the tetrahedral order (q) of water is also decreased and its favorite distribution peak moves from 0.76 to 0.5. In addition, the orientational freedom k and the diffusion coefficient D of water molecules are reduced because of new formed hydrogen-bonding structures between water and solvated ions.

Lattice damage assessment and optical waveguide properties in LaAlO3 single crystal irradiated with swift Si ions

NASA Astrophysics Data System (ADS)

Liu, Y.; Crespillo, M. L.; Huang, Q.; Wang, T. J.; Liu, P.; Wang, X. L.

2017-02-01

As one of the representative ABO3 perovskite-structured oxides, lanthanum aluminate (LaAlO3) crystal has emerged as one of the most valuable functional-materials, and has attracted plenty of fundamental research and promising applications in recent years. Electronic, magnetic, optical and other properties of LaAlO3 strongly depend on its crystal structure, which could be strongly modified owing to the nuclear or electronic energy loss deposited in an ion irradiation environment and, therefore, significantly affecting the performance of LaAlO3-based devices. In this work, utilizing swift (tens of MeV) Si-ion irradiation, the damage behavior of LaAlO3 crystal induced by nuclear or electronic energy loss has been studied in detail utilizing complementary characterization techniques. Differing from other perovskite-structured crystals in which the electronic energy loss could lead to the formation of an amorphous region based on the thermal spike mechanism, in this case, intense electronic energy loss in LaAlO3 will not induce any obvious structural damage. The effects of ion irradiation on the mechanical properties, including hardness increase and elastic modulus decrease, have been confirmed. On the other hand, considering the potential applications of LaAlO3 in the field of integrated optoelectronics, the optical-waveguide properties of the irradiation region have been studied. The significant correspondence (symmetrical inversion) between the iWKB-reconstructed refractive-index profile and SRIM-simulated dpa profile further proves the effects (irradiation-damage production and refractive-index decrease) of nuclear energy loss during the swift-ion penetration process in LaAlO3 crystal. In the case of the rather-thick damage layer produced by swift-ion irradiation, obtaining a damage profile will be constrained owing to the analysis-depth limitation of the characterization techniques (RBS/channeling), and our analysis process (optical guided-mode measurement and subsequent refractive-index-profile reconstruction) also provides a new approach to study the damage behavior (damage profile) once the functional relationship between the refractive index and lattice disorder for the specific material could be determined.

Intricate Hollow Structures: Controlled Synthesis and Applications in Energy Storage and Conversion.

PubMed

Zhou, Liang; Zhuang, Zechao; Zhao, Huihui; Lin, Mengting; Zhao, Dongyuan; Mai, Liqiang

2017-05-01

Intricate hollow structures garner tremendous interest due to their aesthetic beauty, unique structural features, fascinating physicochemical properties, and widespread applications. Here, the recent advances in the controlled synthesis are discussed, as well as applications of intricate hollow structures with regard to energy storage and conversion. The synthetic strategies toward complex multishelled hollow structures are classified into six categories, including well-established hard- and soft-templating methods, as well as newly emerging approaches based on selective etching of "soft@hard" particles, Ostwald ripening, ion exchange, and thermally induced mass relocation. Strategies for constructing structures beyond multishelled hollow structures, such as bubble-within-bubble, tube-in-tube, and wire-in-tube structures, are also covered. Niche applications of intricate hollow structures in lithium-ion batteries, Li-S batteries, supercapacitors, Li-O 2 batteries, dye-sensitized solar cells, photocatalysis, and fuel cells are discussed in detail. Some perspectives on the future research and development of intricate hollow structures are also provided. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural modifications induced by ion irradiation and temperature in boron carbide B4C

NASA Astrophysics Data System (ADS)

Victor, G.; Pipon, Y.; Bérerd, N.; Toulhoat, N.; Moncoffre, N.; Djourelov, N.; Miro, S.; Baillet, J.; Pradeilles, N.; Rapaud, O.; Maître, A.; Gosset, D.

2015-12-01

Already used as neutron absorber in the current French nuclear reactors, boron carbide (B4C) is also considered in the future Sodium Fast Reactors of the next generation (Gen IV). Due to severe irradiation conditions occurring in these reactors, it is of primary importance that this material presents a high structural resistance under irradiation, both in the ballistic and electronic damage regimes. Previous works have shown an important structural resistance of boron carbide even at high neutron fluences. Nevertheless, the structural modification mechanisms due to irradiation are not well understood. Therefore the aim of this paper is to study structural modifications induced in B4C samples in different damage regimes. The boron carbide pellets were shaped and sintered by using spark plasma sintering method. They were then irradiated in several conditions at room temperature or 800 °C, either by favoring the creation of ballistic damage (between 1 and 3 dpa), or by favoring the electronic excitations using 100 MeV swift iodine ions (Se ≈ 15 keV/nm). Ex situ micro-Raman spectroscopy and Doppler broadening of annihilation radiation technique with variable energy slow positrons were coupled to follow the evolution of the B4C structure under irradiation.

Lattice modification in KTiOPO4 by hydrogen and helium sequentially implantation in submicrometer depth

NASA Astrophysics Data System (ADS)

Ma, Changdong; Lu, Fei; Xu, Bo; Fan, Ranran

2016-05-01

We investigated lattice modification and its physical mechanism in H and He co-implanted, z-cut potassium titanyl phosphate (KTiOPO4). The samples were implanted with 110 keV H and 190 keV He, both to a fluence of 4 × 1016 cm-2, at room temperature. Rutherford backscattering/channeling, high-resolution x-ray diffraction, and transmission electron microscopy were used to examine the implantation-induced structural changes and strain. Experimental and simulated x-ray diffraction results show that the strain in the implanted KTiOPO4 crystal is caused by interstitial atoms. The strain and stress are anisotropic and depend on the crystal's orientation. Transmission electron microscopy studies indicate that ion implantation produces many dislocations in the as-implanted samples. Annealing can induce ion aggregation to form nanobubbles, but plastic deformation and ion out-diffusion prevent the KTiOPO4 surface from blistering.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Changdong; Department of Radiation Oncology, Qilu Hospital, Shandong University, Jinan, Shandong 250012; Lu, Fei, E-mail: lufei@sdu.edu.cn

We investigated lattice modification and its physical mechanism in H and He co-implanted, z-cut potassium titanyl phosphate (KTiOPO{sub 4}). The samples were implanted with 110 keV H and 190 keV He, both to a fluence of 4 × 10{sup 16 }cm{sup −2}, at room temperature. Rutherford backscattering/channeling, high-resolution x-ray diffraction, and transmission electron microscopy were used to examine the implantation-induced structural changes and strain. Experimental and simulated x-ray diffraction results show that the strain in the implanted KTiOPO{sub 4} crystal is caused by interstitial atoms. The strain and stress are anisotropic and depend on the crystal's orientation. Transmission electron microscopy studies indicate that ion implantationmore » produces many dislocations in the as-implanted samples. Annealing can induce ion aggregation to form nanobubbles, but plastic deformation and ion out-diffusion prevent the KTiOPO{sub 4} surface from blistering.« less

Control of domain wall pinning by localised focused Ga {sup +} ion irradiation on Au capped NiFe nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burn, D. M., E-mail: d.burn@imperial.ac.uk; Atkinson, D.

2014-10-28

Understanding domain wall pinning and propagation in nanowires are important for future spintronics and nanoparticle manipulation technologies. Here, the effects of microscopic local modification of the magnetic properties, induced by focused-ion-beam intermixing, in NiFe/Au bilayer nanowires on the pinning behavior of domain walls was investigated. The effects of irradiation dose and the length of the irradiated features were investigated experimentally. The results are considered in the context of detailed quasi-static micromagnetic simulations, where the ion-induced modification was represented as a local reduction of the saturation magnetization. Simulations show that domain wall pinning behavior depends on the magnitude of the magnetizationmore » change, the length of the modified region, and the domain wall structure. Comparative analysis indicates that reduced saturation magnetisation is not solely responsible for the experimentally observed pinning behavior.« less

Gyrokinetic particle simulation of beta-induced Alfven-acoustic eigenmode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, H. S., E-mail: zhang.huasen@gmail.com; Institute of Applied Physics and Computational Mathematics, Beijing 100088; Liu, Y. Q.

2016-04-15

The beta-induced Alfven-acoustic eigenmode (BAAE) in toroidal plasmas is verified and studied by global gyrokinetic particle simulations. When ion temperature is much lower than electron temperature, the existence of the weakly damped BAAE is verified in the simulations using initial perturbation, antenna excitation, and energetic particle excitation, respectively. When the ion temperature is comparable to the electron temperature, the unstable BAAE can be excited by realistic energetic particle density gradient, even though the stable BAAE (in the absence of energetic particles) is heavily damped by the thermal ions. In the simulations with reversed magnetic shear, BAAE frequency sweeping is observedmore » and poloidal mode structure has a triangle shape with a poloidal direction similar to that observed in tokamak experiments. The triangle shape changes the poloidal direction, and no frequency sweeping is found in the simulations with normal magnetic shear.« less

Facile fabrication of multilayer separators for lithium-ion battery via multilayer coextrusion and thermal induced phase separation

NASA Astrophysics Data System (ADS)

Li, Yajie; Pu, Hongting

2018-04-01

Polypropylene (PP)/polyethylene (PE) multilayer separators with cellular-like submicron pore structure for lithium-ion battery are efficiently fabricated by the combination of multilayer coextrusion (MC) and thermal induced phase separation (TIPS). The as-prepared separators, referred to as MC-TIPS PP/PE, not only show efficacious thermal shutdown function and wider shutdown temperature window, but also exhibit higher thermal stability than the commercial separator with trilayer construction of PP and PE (Celgard® 2325). The dimensional shrinkage of MC-TIPS PP/PE can be negligible until 160 °C. In addition, compared to the commercial separator, MC-TIPS PP/PE exhibits higher porosity and electrolyte uptake, leading to higher ionic conductivity and better battery performances. The above-mentioned fascinating characteristics with the convenient preparation process make MC-TIPS PP/PE a promising candidate for the application as high performance lithium-ion battery separators.

Highly periodic laser-induced nanostructures on thin Ti and Cu foils for potential application in laser ion acceleration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Susanta Kumar, E-mail: skdasfpy@kiit.ac.in; Andreev, Alexander; Braenzel, Julia

2016-03-21

The feasibility of femtosecond laser-induced periodic nanostructures on thin Ti and Cu foils (thickness down to 1 μm) is demonstrated. At pulse durations of 120 fs and a wavelength of 400 nm, periods of 61 nm to 320 nm were obtained. Particle-in-cell simulations of laser ion acceleration processes with such nanostructured targets indicate their potential for high energy particle physics applications. In particular, a measurable enhancement of the proton cut-off energy and a significant enhancement of the number of accelerated particles compared to non- or weakly structured targets of same thickness and material are expected.

Modification of optical and electrical properties of zinc oxide-coated porous silicon nanostructures induced by swift heavy ion

PubMed Central

2012-01-01

Morphological and optical characteristics of radio frequency-sputtered zinc aluminum oxide over porous silicon (PS) substrates were studied before and after irradiating composite films with 130 MeV of nickel ions at different fluences varying from 1 × 1012 to 3 × 1013 ions/cm2. The effect of irradiation on the composite structure was investigated by scanning electron microscopy, X-ray diffraction (XRD), photoluminescence (PL), and cathodoluminescence spectroscopy. Current–voltage characteristics of ZnO-PS heterojunctions were also measured. As compared to the granular crystallites of zinc oxide layer, Al-doped zinc oxide (ZnO) layer showed a flaky structure. The PL spectrum of the pristine composite structure consists of the emission from the ZnO layer as well as the near-infrared emission from the PS substrate. Due to an increase in the number of deep-level defects, possibly oxygen vacancies after swift ion irradiation, PS-Al-doped ZnO nanocomposites formed with high-porosity PS are shown to demonstrate a broadening in the PL emission band, leading to the white light emission. The broadening effect is found to increase with an increase in the ion fluence and porosity. XRD study revealed the relative resistance of the film against the irradiation, i.e., the irradiation of the structure failed to completely amorphize the structure, suggesting its possible application in optoelectronics and sensing applications under harsh radiation conditions. PMID:22748164

Progress report on nuclear spectroscopic studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.

1994-02-18

The Nuclear Physics group at the University of Tennessee, Knoxville (UTK) is involved in several aspects of heavy-ion physics including both nuclear structure and reaction mechanisms. While the main emphasis is on experimental problems, the authors have maintained a strong collaboration with several theorists in order to best pursue the physics of their measurements. During the last year they have had several experiments at the ATLAS at Argonne National Laboratory, the GAMMASPHERE at the LBL 88 Cyclotron, and with the NORDBALL at the Niels Bohr Institute Tandem. Also, they continue to be very active in the WA93/98 collaboration studying ultra-relativisticmore » heavy ion physics utilizing the SPS accelerator at CERN in Geneva, Switzerland and in the PHENIX Collaboration at the RHIC accelerator under construction at Brookhaven National Laboratory. During the last year their experimental work has been in three broad areas: (1) the structure of nuclei at high angular momentum, (2) the structure of nuclei far from stability, and (3) ultra-relativistic heavy-ion physics. The results of studies in these particular areas are described in this document. These studies concentrate on the structure of nuclear matter in extreme conditions of rotational motion, imbalance of neutrons and protons, or very high temperature and density. Another area of research is heavy-ion-induced transfer reactions, which utilize the transfer of nucleons to states with high angular momentum to learn about their structure and to understand the transfer of particles, energy, and angular momentum in collisions between heavy ions.« less

Alignment and Imaging of the CS2 Dimer Inside Helium Nanodroplets

NASA Astrophysics Data System (ADS)

Pickering, James D.; Shepperson, Benjamin; Hübschmann, Bjarke A. K.; Thorning, Frederik; Stapelfeldt, Henrik

2018-03-01

The carbon disulphide (CS2) dimer is formed inside He nanodroplets and identified using fs laser-induced Coulomb explosion, by observing the CS2+ ion recoil velocity. It is then shown that a 160 ps moderately intense laser pulse can align the dimer in advantageous spatial orientations which allow us to determine the cross-shaped structure of the dimer by analysis of the correlations between the emission angles of the nascent CS2+ and S+ ions, following the explosion process. Our method will enable fs time-resolved structural imaging of weakly bound molecular complexes during conformational isomerization, including formation of exciplexes.

Research Update: Fast and tunable nanoionics in vertically aligned nanostructured films

NASA Astrophysics Data System (ADS)

Lee, Shinbuhm; MacManus-Driscoll, Judith L.

2017-04-01

This review provides the design principles to develop new nanoionic applications using vertically aligned nanostructured (VAN) thin films, incorporating two phases which self-assemble in one film. Tunable nanoionics has attracted great attention for energy and device applications, such as ion batteries, solid oxide fuel cells, catalysts, memories, and neuromorphic devices. Among many proposed device architectures, VAN films have strong potential for nanoionic applications since they show enhanced ionic conductivity and tunability. Here, we will review the recent progress on state-of-the-art nanoionic applications, which have been realized by using VAN films. In many VAN systems made by the inclusion of an oxygen ionic insulator, it is found that ions flow through the vertical heterointerfaces. The observation is consistent with structural incompatibility at the vertical heteroepitaxial interfaces resulting in oxygen deficiency in one of the phases and hence to oxygen ion conducting pathways. In other VAN systems where one of the phases is an ionic conductor, ions flow much faster within the ionic conducting phase than within the corresponding plain film. The improved ionic conduction coincides with much improved crystallinity in the ionically conducting nanocolumnar phase, induced by use of the VAN structure. Furthermore, for both cases Joule heating effects induced by localized ionic current flow also play a role for enhanced ionic conductivity. Nanocolumn stoichiometry and strain are other important parameters for tuning ionic conductivity in VAN films. Finally, double-layered VAN film architectures are discussed from the perspective of stabilizing VAN structures which would be less stable and hence less perfect when grown on standard substrates.

Ozone-Induced Dissociation of Conjugated Lipids Reveals Significant Reaction Rate Enhancements and Characteristic Odd-Electron Product Ions

NASA Astrophysics Data System (ADS)

Pham, Huong T.; Maccarone, Alan T.; Campbell, J. Larry; Mitchell, Todd W.; Blanksby, Stephen J.

2013-02-01

Ozone-induced dissociation (OzID) is an alternative ion activation method that relies on the gas phase ion-molecule reaction between a mass-selected target ion and ozone in an ion trap mass spectrometer. Herein, we evaluated the performance of OzID for both the structural elucidation and selective detection of conjugated carbon-carbon double bond motifs within lipids. The relative reactivity trends for [M + X]+ ions (where X = Li, Na, K) formed via electrospray ionization (ESI) of conjugated versus nonconjugated fatty acid methyl esters (FAMEs) were examined using two different OzID-enabled linear ion-trap mass spectrometers. Compared with nonconjugated analogues, FAMEs derived from conjugated linoleic acids were found to react up to 200 times faster and to yield characteristic radical cations. The significantly enhanced reactivity of conjugated isomers means that OzID product ions can be observed without invoking a reaction delay in the experimental sequence (i.e., trapping of ions in the presence of ozone is not required). This possibility has been exploited to undertake neutral-loss scans on a triple quadrupole mass spectrometer targeting characteristic OzID transitions. Such analyses reveal the presence of conjugated double bonds in lipids extracted from selected foodstuffs. Finally, by benchmarking of the absolute ozone concentration inside the ion trap, second order rate constants for the gas phase reactions between unsaturated organic ions and ozone were obtained. These results demonstrate a significant influence of the adducting metal on reaction rate constants in the fashion Li > Na > K.

Poincaré analysis of wave motion in ultrarelativistic electron-ion plasmas.

PubMed

Lehmann, G; Spatschek, K H

2011-03-01

Based on a relativistic Maxwell-fluid description, the existence of ultrarelativistic laser-induced periodic waves in an electron-ion plasma is investigated. Within a one-dimensional propagation geometry nonlinear coupling of the electromagnetic and electrostatic components occurs that makes the fourth-order problem nonintegrable. A Hamiltonian description is derived, and the manifolds of periodic solutions are studied by Poincaré section plots. The influence of ion motion is investigated in different intensity regimes. For ultrarelativistic laser intensities the phase-space structures change significantly compared to the weakly relativistic case. Ion motion becomes very important such that finally electron-ion plasmas in the far-ultrarelativistic regime behave similarly to electron-positron plasmas. The characteristic new types of periodic solutions of the system are identified and discussed.

High Electrochemical Sensitivity of TiO2- x Nanosheets and an Electron-Induced Mutual Interference Effect toward Heavy Metal Ions Demonstrated Using X-ray Absorption Fine Structure Spectra.

PubMed

Zhou, Wen-Yi; Li, Shan-Shan; Song, Jie-Yao; Jiang, Min; Jiang, Tian-Jia; Liu, Jin-Yun; Liu, Jin-Huai; Huang, Xing-Jiu

2018-04-03

Mutual interference is a severe issue that occurs during the electrochemical detection of heavy metal ions. This limitation presents a notable drawback for its high sensitivity to specific targets. Here, we present a high electrochemical sensitivity of ∼237.1 μA cm -2 μM -1 toward copper(II) [Cu(II)] based on oxygen-deficient titanium dioxide (TiO 2- x ) nanosheets. We fully demonstrated an atomic-level relationship between electrochemical behaviors and the key factors, including the high-energy (001) facet percentage, oxygen vacancy concentration, surface -OH content, and charge carrier density, is fully demonstrated. These four factors were quantified using Raman, electron spin resonance, X-ray photoelectron spectroscopy spectra, and Mott-Schottky plots. In the mutual interference investigation, we selected cadmium(II) [Cd(II)] as the target ion because of the significant difference in its stripping potential (∼700 mV). The results show that the Cd(II) can enhance the sensitivity of TiO 2- x nanosheets toward Cu(II), exhibiting an electron-induced mutual interference effect, as demonstrated by X-ray absorption fine structure spectra.

Alkyl ether lipids, ion channels and lipid raft reorganization in cancer therapy.

PubMed

Jaffrès, Paul-Alain; Gajate, Consuelo; Bouchet, Ana Maria; Couthon-Gourvès, Hélène; Chantôme, Aurélie; Potier-Cartereau, Marie; Besson, Pierre; Bougnoux, Philippe; Mollinedo, Faustino; Vandier, Christophe

2016-09-01

Synthetic alkyl lipids, such as the ether lipids edelfosine (1-O-octadecyl-2-O-methyl-rac-glycero-3-phosphocholine) and ohmline (1-O-hexadecyl-2-O-methyl-rac-glycero-3-β-lactose), are forming a class of antitumor agents that target cell membranes to induce apoptosis and to decrease cell migration/invasion, leading to the inhibition of tumor and metastasis development. In this review, we present the structure-activity relationship of edelfosine and ohmline, and we point out differences and similarities between these two amphiphilic compounds. We also discuss the mechanisms of action of these synthetic alkyl ether lipids (involving, among other structures and molecules, membrane domains, Fas/CD95 death receptor signaling, and ion channels), and highlight a key role for lipid rafts in the underlying process. The reorganization of lipid raft membrane domains induced by these alkyl lipids affects the function of death receptors and ion channels, thus leading to apoptosis and/or inhibition of cancer cell migration. The possible therapeutic use of these alkyl lipids and the clinical perspectives for these lipids in prevention or/and treatment of tumor development and metastasis are also discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

Structural analysis of N-glycans by the glycan-labeling method using 3-aminoquinoline-based liquid matrix in negative-ion MALDI-MS.

PubMed

Nishikaze, Takashi; Kaneshiro, Kaoru; Kawabata, Shin-ichirou; Tanaka, Koichi

2012-11-06

Negative-ion fragmentation of underivatized N-glycans has been proven to be more informative than positive-ion fragmentation. Fluorescent labeling via reductive amination is often employed for glycan analysis, but little is known about the influence of the labeling group on negative-ion fragmentation. We previously demonstrated that the on-target glycan-labeling method using 3-aminoquinoline/α-cyano-4-hydroxycinnamic acid (3AQ/CHCA) liquid matrix enables highly sensitive, rapid, and quantitative N-glycan profiling analysis. The current study investigates the suitability of 3AQ-labeled N-glycans for structural analysis based on negative-ion collision-induced dissociation (CID) spectra. 3AQ-labeled N-glycans exhibited simple and informative CID spectra similar to those of underivatized N-glycans, with product ions due to cross-ring cleavages of the chitobiose core and ions specific to two antennae (D and E ions). The interpretation of diagnostic fragment ions suggested for underivatized N-glycans could be directly applied to the 3AQ-labeled N-glycans. However, fluorescently labeled N-glycans by conventional reductive amination, such as 2-aminobenzamide (2AB)- and 2-pyrydilamine (2PA)-labeled N-glycans, exhibited complicated CID spectra consisting of numerous signals formed by dehydration and multiple cleavages. The complicated spectra of 2AB- and 2PA-labeled N-glycans was found to be due to their open reducing-terminal N-acetylglucosamine (GlcNAc) ring, rather than structural differences in the labeling group in the N-glycan derivative. Finally, as an example, the on-target 3AQ labeling method followed by negative-ion CID was applied to structurally analyze neutral N-glycans released from human epidermal growth factor receptor type 2 (HER2) protein. The glycan-labeling method using 3AQ-based liquid matrix should facilitate highly sensitive quantitative and qualitative analyses of glycans.

Environment and Structure Influence in DNA Conduction

NASA Technical Reports Server (NTRS)

Adessi, C.; Walch, S.; Anantram, M. P.; Biegel, Bryan (Technical Monitor)

2002-01-01

Results for transmission through the poly(G) DNA molecule are presented. We show that (i) periodically arranged sodium counter-ions in close proximity to dry DNA gives rise to a new conduction channel and aperiodicity in the counter-ion sequence can lead to a significant reduction in conduction, (ii) modification of the rise of B-DNA induces a change in the width of the transmission window, and (iii) specifically designed sequences are predicted to show intrinsic resonant tunneling behavior.

3D-structured illumination microscopy reveals clustered DNA double-strand break formation in widespread γH2AX foci after high LET heavy-ion particle radiation.

PubMed

Hagiwara, Yoshihiko; Niimi, Atsuko; Isono, Mayu; Yamauchi, Motohiro; Yasuhara, Takaaki; Limsirichaikul, Siripan; Oike, Takahiro; Sato, Hiro; Held, Kathryn D; Nakano, Takashi; Shibata, Atsushi

2017-12-12

DNA double-strand breaks (DSBs) induced by ionising radiation are considered the major cause of genotoxic mutations and cell death. While DSBs are dispersed throughout chromatin after X-rays or γ-irradiation, multiple types of DNA damage including DSBs, single-strand breaks and base damage can be generated within 1-2 helical DNA turns, defined as a complex DNA lesion, after high Linear Energy Transfer (LET) particle irradiation. In addition to the formation of complex DNA lesions, recent evidence suggests that multiple DSBs can be closely generated along the tracks of high LET particle irradiation. Herein, by using three dimensional (3D)-structured illumination microscopy, we identified the formation of 3D widespread γH2AX foci after high LET carbon-ion irradiation. The large γH2AX foci in G 2 -phase cells encompassed multiple foci of replication protein A (RPA), a marker of DSBs undergoing resection during homologous recombination. Furthermore, we demonstrated by 3D analysis that the distance between two individual RPA foci within γH2AX foci was approximately 700 nm. Together, our findings suggest that high LET heavy-ion particles induce clustered DSB formation on a scale of approximately 1 μm 3 . These closely localised DSBs are considered to be a risk for the formation of chromosomal rearrangement after heavy-ion irradiation.

Valence, exchange interaction, and location of Mn ions in polycrystalline M nxG a1 -xN (x ≤0.04 )

NASA Astrophysics Data System (ADS)

Furrer, A.; Krämer, K. W.; Podlesnyak, A.; Pomjakushin, V.; Sheptyakov, D.; Safonova, O. V.

2018-04-01

We present an experimental study for polycrystalline samples of the diluted magnetic semiconductor M nxG a1 -xN (x ≤0.04 ) in order to address some of the existing controversial issues. X-ray and neutron diffraction, x-ray absorption near-edge structure, and electron paramagnetic resonance experiments were used to characterize the structural, electronic, and magnetic properties of the samples, and inelastic neutron scattering was employed to determine the magnetic excitations associated with Mn monomers and dimers. Our main conclusions are as follows: (i) The valence of the Mn ions is 2 + . (ii) The M n2 + ions experience a substantial single-ion axial anisotropy with parameter D =0.027 (3 )meV . (iii) Nearest-neighbor M n2 + ions are coupled antiferromagnetically. The exchange parameter J =-0.140 (7 )meV is independent of the Mn content x ; i.e., there is no evidence for hole-induced modifications of J towards a potentially high Curie temperature postulated in the literature.

Sodium effect on self-organization of amphiphilic carboxylates: formation of structured micelles and superlattices.

PubMed

Rosenlehner, Karin; Schade, Boris; Böttcher, Christoph; Jäger, Christof M; Clark, Timothy; Heinemann, Frank W; Hirsch, Andreas

2010-08-16

Not only the self-aggregation of dendritic polycarboxylates into structurally persistent micelles, but also that of the micelles themselves into superlattices is controlled by alkali-metal counterions and shows a pronounced sodium effect. Our combined experimental and computational work has revealed the formation of superlattices for the first time. The behavior of a variety of amphiphilic carboxylates and the different effects of the alkali cations Li(+), Na(+), and K(+) have been investigated by conductivity measurements, cryogenic transmission electron microscopy (cryo-TEM), and molecular-dynamics (MD) simulations. Together, these show that sodium salts of the amphiphiles give the most stable micelles, followed by lithium and potassium. Our results suggest that ion multiplets in bridging positions, rather than contact ion pairs, are responsible for the enhanced stability and the formation of hexagonally ordered superlattices with sodium counterions. Potassium ions do not form such ion multiplets and cannot therefore induce aggregation of the micelles. This sodium effect has far-reaching consequences for a large number of biological and technical systems and sheds new light on the origin of specific-ion effects.

Photoluminescence and reflectivity of polymethylmethacrylate implanted by low-energy carbon ions at high fluences

NASA Astrophysics Data System (ADS)

Wang, Jun; Zhu, Fei; Zhang, Bei; Liu, Huixian; Jia, Guangyi; Liu, Changlong

2012-11-01

Polymethylmethacrylate (PMMA) specimens were implanted with 30 keV carbon ions in a fluence range of 1 × 1016 to 2 × 1017 cm-2, and photoluminescence (PL) and reflectivity of the implanted samples were examined. A luminescent band with one peak was found in PL spectra excited by 480 nm line, but its intensity did not vary in parallel with ion fluence. The strongest PL occurred at the fluence of 5 × 1016 cm-2. Results from visible-light-excited micro-Raman spectra indicated that the formation of hydrogenated amorphous carbon structures in subsurface layer and their evolutions with ion fluence could be responsible for the observed PL responses. Measurements of the small-angle reflectance spectra from both the implanted and rear surfaces of samples in the ultraviolet-visible (UV-vis) range demonstrated a kind of both fluence-dependent and wavelength-related reflectivity variations, which were attributed to the structural changes induced by ion implantation. A noticeable reflectivity modification, which may be practically used, could be found at the fluence of 1 × 1016 cm-2.

Multi-instrumental Analysis of Tissues of Sunflower Plants Treated with Silver(I) Ions – Plants as Bioindicators of Environmental Pollution

PubMed Central

Krizkova, Sona; Ryant, Pavel; Krystofova, Olga; Adam, Vojtech; Galiova, Michaela; Beklova, Miroslava; Babula, Petr; Kaiser, Jozef; Novotny, Karel; Novotny, Jan; Liska, Miroslav; Malina, Radomir; Zehnalek, Josef; Hubalek, Jaromir; Havel, Ladislav; Kizek, Rene

2008-01-01

The aim of this work is to investigate sunflower plants response on stress induced by silver(I) ions. The sunflower plants were exposed to silver(I) ions (0, 0.1, 0.5, and 1 mM) for 96 h. Primarily we aimed our attention to observation of basic physiological parameters. We found that the treated plants embodied growth depression, coloured changes and lack root hairs. Using of autofluorescence of anatomical structures, such as lignified cell walls, it was possible to determine the changes of important shoot and root structures, mainly vascular bungles and development of secondary thickening. The differences in vascular bundles organisation, parenchymatic pith development in the root centre and the reduction of phloem part of vascular bundles were well observable. Moreover with increasing silver(I) ions concentration the vitality of rhizodermal cells declined; rhizodermal cells early necrosed and were replaced by the cells of exodermis. Further we employed laser induced breakdown spectroscopy for determination of spatial distribution of silver(I) ions in tissues of the treated plants. The Ag is accumulated mainly in near-root part of the sample. Moreover basic biochemical indicators of environmental stress were investigated. The total content of proteins expressively decreased with increasing silver(I) ions dose and the time of the treatment. As we compare the results obtained by protein analysis – the total protein contents in shoot as well as root parts – we can assume on the transport of the proteins from the roots to shoots. This phenomenon can be related with the cascade of processes connecting with photosynthesis. The second biochemical parameter, which we investigated, was urease activity. If we compared the activity in treated plants with control, we found out that presence of silver(I) ions markedly enhanced the activity of urease at all applied doses of this toxic metal. Finally we studied the effect of silver(I) ions on activity of urease in in vitro conditions. PMID:27879716

Surface chemical reactions induced on pyrite by ion bombardment

NASA Astrophysics Data System (ADS)

Ruano, Gustavo; Pomiro, Fernando; Ferrón, Julio

2018-01-01

Through X-ray photoemission spectroscopy (XPS), we studied the chemical changes induced in a natural crystal of pyrite (FeS2) upon exposure to 4.5 keV He+ beam. We found an important reducing effect induced by ion bombardment leading to the production of iron embedded in the pyrite matrix. Through a combination of the usual Doniach-Sunjic treatment and Factor Analysis of XPS yields, we were able of analyzing the full Fe 2p XPS signal. We could in this way distinguish Fe compounds with the same binding energy for the Fe 2p3/2 yield. Our results show that He+ bombardment disrupts the ionic environment producing S2-2 and S0, Fe2+ and Fe3+ ions, and the reduction to metallic iron. The remaining pyrite matrix does not passivate the embedded iron structures, which are readily oxidized under air exposure. The oxide formed resembled that of magnetite from the XPS point of view. Further He+ bombardment proved to be efficient to reduce the iron oxide back to iron again.

Study of change of hydrophysical properties of bore mud in process of its utilization into man-induced soil

NASA Astrophysics Data System (ADS)

Gaevaya, E. V.; Bogaychuk, Y. E.; Tarasova, S. S.; Skipin, L. N.; Zaharova, E. V.

2017-10-01

The article considers the results of studies of the chemical and granulometric content and the factor of bore mud filtration in the process of its utilization. When the phosphogypsum is added, hydrophysical properties of the bore mud improve. At the same time, gradation of soil from the water-proof to weakly permeable takes place. This phenomenon is connected with recovery of filterability at the expense of ion-exchange reaction and a decrease of the silt fraction content in the bore mud. During the adding of phosphogypsum in the bore mud, pH decreased and made up 7.6-7.8 U. The decrease of the concentration of chloride-ions and sulphate-ions took place at the expense of replacement of Na+ by cations of Ca2+ that contributed to the formation of the water-stable structure with good filterability. The content of total forms of heavy metals in man-induced soil was lower than MAC (APC) for the loams. Man-induced soil has a V class of danger for the surrounding environment.

Structure effects on reaction mechanisms in collisions induced by radioactive ion beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pietro, A. Di, E-mail: dipietro@lns.infn.it; Figuera, P.; Scuderi, V.

2006-08-15

The present paper concerns the study of reactions induced by radioactive beams of halo and weakly bound nuclei at energies around and above the Coulomb barrier. The results obtained for the reaction induced by the halo nucleus {sup 6}He on {sup 64}Zn have been compared with the results for the reaction induced by {sup 4}He on the same target. The results of the reaction induced by the weakly bound unstable {sup 13}N on the weakly bound {sup 9}Be have been compared with those for the reaction {sup 10}B + {sup 12}C.

Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhiguo; He, Yang; Gu, Meng

2016-09-21

Reversible insertion/extraction of ions into a host lattice constitutes the fundamental operating principle of rechargeable battery and electrochromic materials. It is far more commonly observed that insertion of ions into a host lattice can lead to structural evolution of the host lattice, and for the most cases such a lattice evolution is subtle. However, it has never been clear as what kind of factors to control such a lattice structural evolution. Based on tungsten trioxide (WO3) model crystal, we use in situ transmission electron microscopy (TEM) and first principles calculation to explore the nature of Li ions intercalation induced crystalmore » symmetry evolution of WO3. We discovered that Li insertion into the octahedral cavity of WO3 lattice will lead to a low to high symmetry transition, featuring a sequential monoclinic→tetragonal→cubic phase transition. The first principle calculation reveals that the phase transition is essentially governed by the electron transfer from Li to the WO6 octahedrons, which effectively leads to the weakening the W-O bond and modifying system band structure, resulting in an insulator to metal transition. The observation of the electronic effect on crystal symmetry and conductivity is significant, providing deep insights on the intercalation reactions in secondary rechargeable ion batteries and the approach for tailoring the functionalities of material based on insertion of ions in the lattice.« less

Electronic excitation induced modifications of structural, electrical and optical properties of Cu-C60 nanocomposite thin films

NASA Astrophysics Data System (ADS)

Inani, H.; Singhal, R.; Sharma, P.; Vishnoi, R.; Ojha, S.; Chand, S.; Sharma, G. D.

2017-09-01

High energy ion irradiation significantly affects the size and shape of nanoparticles in composites. Low concentration metal fraction embedded in fullerene matrix in form of nanocomposites was synthesized by thermal co-evaporation method. Swift heavy ion irradiation was performed with 120 MeV Au ion beam on Cu-C60 nanocomposites at different fluences 1 × 1012, 3 × 1012, 6 × 1012, 1 × 1013 and 3 × 1013 ions/cm2. Absorption spectra demonstrated that absorption intensity of nanocomposite thin film was increased whereas absorption modes of fullerene C60 were diminished with fluence. Rutherford backscattering spectroscopy was also performed to estimate the thickness of the film and atomic metal fraction in matrix and found to be 45 nm and 3%, respectively. Transmission electron microscopy was performed for structural and particle size evaluation of Cu nanoparticles (NPs) in fullerene C60 matrix. A growth of Cu nanoparticles is observed at a fluence of 3 × 1013 ions/cm2 with a bi-modal distribution in fullerene C60. Structural evolution of fullerene C60 matrix with increasing fluence of 120 MeV Au ion beam is studied by Raman spectroscopy which shows the amorphization of matrix (fullerene C60) at lower fluence. The growth of Cu nanoparticles is explained using the phenomena of Ostwald ripening.

Structural Information Inference from Lanthanoid Complexing Systems: Photoluminescence Studies on Isolated Ions

NASA Astrophysics Data System (ADS)

Greisch, Jean Francois; Harding, Michael E.; Chmela, Jiri; Klopper, Willem M.; Schooss, Detlef; Kappes, Manfred M.

2016-06-01

The application of lanthanoid complexes ranges from photovoltaics and light-emitting diodes to quantum memories and biological assays. Rationalization of their design requires a thorough understanding of intramolecular processes such as energy transfer, charge transfer, and non-radiative decay involving their subunits. Characterization of the excited states of such complexes considerably benefits from mass spectrometric methods since the associated optical transitions and processes are strongly affected by stoichiometry, symmetry, and overall charge state. We report herein spectroscopic measurements on ensembles of ions trapped in the gas phase and soft-landed in neon matrices. Their interpretation is considerably facilitated by direct comparison with computations. The combination of energy- and time-resolved measurements on isolated species with density functional as well as ligand-field and Franck-Condon computations enables us to infer structural as well as dynamical information about the species studied. The approach is first illustrated for sets of model lanthanoid complexes whose structure and electronic properties are systematically varied via the substitution of one component (lanthanoid or alkali,alkali-earth ion): (i) systematic dependence of ligand-centered phosphorescence on the lanthanoid(III) promotion energy and its impact on sensitization, and (ii) structural changes induced by the substitution of alkali or alkali-earth ions in relation with structures inferred using ion mobility spectroscopy. The temperature dependence of sensitization is briefly discussed. The focus is then shifted to measurements involving europium complexes with doxycycline an antibiotic of the tetracycline family. Besides discussing the complexes' structural and electronic features, we report on their use to monitor enzymatic processes involving hydrogen peroxide or biologically relevant molecules such as adenosine triphosphate (ATP).

Mutation induction by heavy ions

NASA Astrophysics Data System (ADS)

Kiefer, J.; Stoll, U.; Schneider, E.

1994-10-01

Mutation induction by heavy ions is compared in yeast and mammalian cells. Since mutants can only be recovered in survivors the influence of inactivation cross sections has to be taken into account. It is shown that both the size of the sensitive cellular site as well as track structure play an important role. Another parameter which influences the probability of mutation induction is repair: Contrary to naive assumptions primary radiation damage does not directly lead to mutations but requires modification to reconstitute the genetic machinery so that mutants can survive. The molecular structure of mutations was analyzed after exposure to deuterons by amplification with the aid of polymerase chain reaction. The results-although preliminary-demonstrate that even with densely ionizing particles a large fraction does not carry big deletions which suggests that point mutations may also be induced by heavy ions.

In situ studies of ion irradiated inverse spinel compound magnesium stannate (Mg 2SnO 4)

NASA Astrophysics Data System (ADS)

Xu, P.; Tang, M.; Nino, J. C.

2009-06-01

Magnesium stannate spinel (Mg 2SnO 4) was synthesized through conventional solid state processing and then irradiated with 1.0 MeV Kr 2+ ions at low temperatures 50 and 150 K. Structural evolutions during irradiation were monitored and recorded through bright field images and selected-area electron diffraction patterns using in situ transmission electron microscopy. The amorphization of Mg 2SnO 4 was achieved at an ion dose of 5 × 10 19 Kr ions/m 2 at 50 K and 10 20 Kr ions/m 2 at 150 K, which is equivalent to an atomic displacement damage of 5.5 and 11.0 dpa, respectively. The spinel crystal structure was thermally recovered at room temperature from the amorphous phase caused by irradiation at 50 K. The calculated electronic and nuclear stopping powers suggest that the radiation damage caused by 1 MeV Kr 2+ ions in Mg 2SnO 4 is mainly due to atomic displacement induced defect accumulation. The radiation tolerance of Mg 2SnO 4 was finally compared with normal spinel MgAl 2O 4.

Formation and characterization of perpendicular mode Si ripples by glancing angle O{sub 2}{sup +} sputtering at room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mollick, S. A.; Ghose, D.

Off-normal low energy ion beam sputtering of solid surfaces often leads to morphological instabilities resulting in the spontaneous formation of ripple structures in nanometer length scales. In the case of Si surfaces at ambient temperature, ripple formation is found to take place normally at lower incident angles with the wave vector parallel to the ion beam direction. The absence of ripple pattern on Si surface at larger angles is due to the dominance of ion beam polishing effect. We have shown that a gentle chemical roughening of the starting surface morphology can initiate ripple pattern under grazing incidence ion beammore » sputtering (theta>64 deg. with respect to the surface normal), where the ripple wave vector is perpendicular to the ion beam direction. The characteristics of the perpendicular mode ripples are studied as a function of pristine surface roughness (2-30 nm) and projectile fluence (5x10{sup 16}-1.5x10{sup 18} O atoms cm{sup -2}). The quality of the morphological structure is assessed from the analysis of ion induced topological defects.« less

First-principles study of strain-induced ferromagnetism in LaCoO3

NASA Astrophysics Data System (ADS)

Seo, Hosung; Demkov, Alexander

2011-03-01

We study theoretically the effect of biaxial strain on magnetic properties of LaCo O3 (LCO) using density functional theory combined with the Hubbard U method. LCO is normally a non-magnetic insulator with trivalent cobalt ions in low-spin state (t 2g 6) . Owing to close interplay between orbital, spin, and lattice degrees of freedom, it shows rich magnetic behavior such as temperature-induced spin state transition. Recently, the ferromagnetic tensile-strained LCO films have been reported. The underlying physics of the ferromagnetic state is, however, unclear. Using a large tetragonal cell we calculate full structural response of the system to applied strain for non-magnetic and magnetic solutions. We show that beyond tensile strain of 3.8% the ferromagnetic solution with Co ions in intermediate-spin state (t 2g 5 e g 1) is stabilized accompanied by partial untilting of Co O6 octahedral network. We also perform the calculation for compressive-strained structures and the difference between these and the tensile strained structures will be presented.

Photovoltaic switching mechanism in lateral structure hybrid perovskite solar cells

DOE PAGES

Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; ...

2015-06-05

In this study, long range electromigration of methylammonium ions (MA +) in methyl ammonium lead tri-iodide (MAPbI 3) film is observed directly using the photo­thermal induced resonance technique. The electromigration of MA + leads to the formation of a lateral p-i-n structure, which is the origin of the switchable photovoltaic effect in MAPbI 3 perovskite devices.

Structural defects caused by swift ions in fluorite single crystals

NASA Astrophysics Data System (ADS)

Assylbayev, Ruslan; Lushchik, Aleksandr; Lushchik, Cheslav; Kudryavtseva, Irina; Shablonin, Evgeni; Vasil'chenko, Evgeni; Akilbekov, Abdirash; Zdorovets, Maxim

2018-01-01

A comparative study of radiation damage caused by the irradiation of oxygen-free calcium fluoride single crystals with ∼GeV 132Xe or 209Bi heavy ions, 100-keV light hydrogen ions (protons) or X-rays at room temperature has been performed. Optical absorption in a wide spectral region from NIR to VUV (1.5-10.5 eV), its dependence on stepwise preheating of the irradiated CaF2 crystals to a certain temperature as well as thermally stimulated luminescence accompanying the main annealing stages have been analyzed. It is shown that in addition to different F-type aggregates, Ca colloids and trifluorine quasi-molecules, complex and temperature stable structural defects responsible for VUV absorption (in particular, the 9.8 eV band) are induced in CaF2 only after irradiation with swift heavy ions. The origin and tentative creation mechanisms of such defects as well as the features of the used irradiation types are considered.

Chloride ions induce order-disorder transition at water-oxide interfaces

NASA Astrophysics Data System (ADS)

Deshmukh, Sanket; Kamath, Ganesh; Ramanathan, Shriram; Sankaranarayanan, Subramanian K. R. S.

2013-12-01

Water can form quasi-two-dimensional ordered layers near a solid interface. The solvation dynamics and ionic transport phenomena through this ordered water structure is of direct relevance to a variety of problems in interface science. Molecular dynamics simulations are used to study the impact of local fluctuation of the chloride ion density in the vicinity of an oxide surface on the structure and dynamics of water layers. We demonstrate that local increase in chloride ions beyond a threshold concentration near the water-MgO (100) interface introduces an order-disorder transition of this two-dimensional layered network into bulklike water, leading to increased diffusional characteristics and reduced hydrogen bonding lifetimes. We find that the extent of this order-disorder transition can be tuned by modifying the defect chemistry and nature of the underlying substrate. The kinetic fluidity resulting from order-disorder transition at high chloride ion concentration has significance for a broad range of phenomena, ranging from freezing point depression of brine to onset of aqueous corrosion.

Effects of nanoparticle heating on the structure of a concentrated aqueous salt solution.

PubMed

Sindt, Julien O; Alexander, Andrew J; Camp, Philip J

2017-12-07

The effects of a rapidly heated nanoparticle on the structure of a concentrated aqueous salt solution are studied using molecular dynamics simulations. A diamond-like nanoparticle of radius 20 Å is immersed in a sodium-chloride solution at 20% above the experimental saturation concentration and equilibrated at T = 293 K and P = 1 atm. The nanoparticle is then rapidly heated to several thousand degrees Kelvin, and the system is held under isobaric-isoenthalpic conditions. It is observed that after 2-3 ns, the salt ions are depleted far more than water molecules from a proximal zone 15-25 Å from the nanoparticle surface. This leads to a transient reduction in molality in the proximal zone and an increase in ion clustering in the distal zone. At longer times, ions begin to diffuse back into the proximal zone. It is speculated that the formation of proximal and distal zones, and the increase in ion clustering, plays a role in the mechanism of nonphotochemical laser-induced nucleation.

Effects of nanoparticle heating on the structure of a concentrated aqueous salt solution

NASA Astrophysics Data System (ADS)

Sindt, Julien O.; Alexander, Andrew J.; Camp, Philip J.

2017-12-01

The effects of a rapidly heated nanoparticle on the structure of a concentrated aqueous salt solution are studied using molecular dynamics simulations. A diamond-like nanoparticle of radius 20 Å is immersed in a sodium-chloride solution at 20% above the experimental saturation concentration and equilibrated at T = 293 K and P = 1 atm. The nanoparticle is then rapidly heated to several thousand degrees Kelvin, and the system is held under isobaric-isoenthalpic conditions. It is observed that after 2-3 ns, the salt ions are depleted far more than water molecules from a proximal zone 15-25 Å from the nanoparticle surface. This leads to a transient reduction in molality in the proximal zone and an increase in ion clustering in the distal zone. At longer times, ions begin to diffuse back into the proximal zone. It is speculated that the formation of proximal and distal zones, and the increase in ion clustering, plays a role in the mechanism of nonphotochemical laser-induced nucleation.

Standardization of accelerator irradiation procedures for simulation of neutron induced damage in reactor structural materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shao, Lin; Gigax, Jonathan; Chen, Di

Self-ion irradiation is widely used as a method to simulate neutron damage in reactor structural materials. Accelerator-based simulation of void swelling, however, introduces a number of neutron-atypical features which require careful data extraction and in some cases introduction of innovative irradiation techniques to alleviate these issues. We briefly summarize three such atypical features: defect imbalance effects, pulsed beam effects, and carbon contamination. The latter issue has just been recently recognized as being relevant to simulation of void swelling and is discussed here in greater detail. It is shown that carbon ions are entrained in the ion beam by Coulomb forcemore » drag and accelerated toward the target surface. Beam-contaminant interactions are modeled using molecular dynamics simulation. By applying a multiple beam deflection technique, carbon and other contaminants can be effectively filtered out, as demonstrated in an irradiation of HT-9 alloy by 3.5 MeV Fe ions.« less

Standardization of accelerator irradiation procedures for simulation of neutron induced damage in reactor structural materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shao, Lin; Gigax, Jonathan; Chen, Di

Self-ion irradiation is widely used as a method to simulate neutron damage in reactor structural materials. Accelerator-based simulation of void swelling, however, introduces a number of neutron-atypical features which require careful data extraction and, in some cases, introduction of innovative irradiation techniques to alleviate these issues. In this paper, we briefly summarize three such atypical features: defect imbalance effects, pulsed beam effects, and carbon contamination. The latter issue has just been recently recognized as being relevant to simulation of void swelling and is discussed here in greater detail. It is shown that carbon ions are entrained in the ion beammore » by Coulomb force drag and accelerated toward the target surface. Beam-contaminant interactions are modeled using molecular dynamics simulation. Finally, by applying a multiple beam deflection technique, carbon and other contaminants can be effectively filtered out, as demonstrated in an irradiation of HT-9 alloy by 3.5 MeV Fe ions.« less

Standardization of accelerator irradiation procedures for simulation of neutron induced damage in reactor structural materials

DOE PAGES

Shao, Lin; Gigax, Jonathan; Chen, Di; ...

2017-06-12

Self-ion irradiation is widely used as a method to simulate neutron damage in reactor structural materials. Accelerator-based simulation of void swelling, however, introduces a number of neutron-atypical features which require careful data extraction and, in some cases, introduction of innovative irradiation techniques to alleviate these issues. In this paper, we briefly summarize three such atypical features: defect imbalance effects, pulsed beam effects, and carbon contamination. The latter issue has just been recently recognized as being relevant to simulation of void swelling and is discussed here in greater detail. It is shown that carbon ions are entrained in the ion beammore » by Coulomb force drag and accelerated toward the target surface. Beam-contaminant interactions are modeled using molecular dynamics simulation. Finally, by applying a multiple beam deflection technique, carbon and other contaminants can be effectively filtered out, as demonstrated in an irradiation of HT-9 alloy by 3.5 MeV Fe ions.« less

Structural analysis of ion-implanted chemical-vapor-deposited diamond by transmission electron microscope

NASA Astrophysics Data System (ADS)

Jiang, N.; Deguchi, M.; Wang, C. L.; Won, J. H.; Jeon, H. M.; Mori, Y.; Hatta, A.; Kitabatake, M.; Ito, T.; Hirao, T.; Sasaki, T.; Hiraki, A.

1997-04-01

A transmission electron microscope (TEM) study of ion-implanted chemical-vapor-deposited (CVD) diamond is presented. CVD diamond used for transmission electron microscope observation was directly deposited onto Mo TEM grids. As-deposited specimens were irradiated by C (100 keV) ions at room temperature with a wide range of implantation doses (10 12-10 17/cm 2). Transmission electron diffraction (TED) patterns indicate that there exists a critical dose ( Dc) for the onset of amorphization of CVD diamond as a result of ion induced damage and the value of critical dose is confirmed to be about 3 × 10 15/cm 2. The ion-induced transformation process is clearly revealed by high resolution electron microscope (HREM) images. For a higher dose implantation (7 × 10 15/cm 2) a large amount of diamond phase is transformed into amorphous carbon and many tiny misoriented diamond blocks are found to be left in the amorphous solid. The average size of these misoriented diamond blocks is only about 1-2 nm. Further bombardment (10 17/cm 2) almost kills all of the diamond phase within the irradiated volume and moreover leads to local formation of micropolycrystalline graphite.

High-Resolution and Analytical TEM Investigation of Space Radiation Processing Effects in Primitive Solar System Materials and Airless Planetary Surface Environments

NASA Technical Reports Server (NTRS)

Christoffersen, R.; Rahman, Z.; Keller, L. P.; Dukes, C.; Baragiola, R.

2012-01-01

Energetic ions present in the diverse plasma conditions in space play a significant role in the formation and modification of solid phases found in environments ranging from the interstellar medium (ISM) to the surfaces of airless bodies such as asteroids and the Moon. These effects are often referred to as space radiation processing, a term that encompasses changes induced in natural space-exposed materials that may be only structural, such as in radiation-induced amorphization, or may involve ion-induced nanoscale to microscale chemical changes, as occurs in preferential sputtering and ion-beam mixing. Ion sputtering in general may also be responsible for partial or complete erosion of space exposed materials, in some instances possibly bringing about the complete destruction of free-floating solid grains in the ISM or in circumstellar nebular dust clouds. We report here on two examples of the application of high-resolution and analytical transmission electron microscopy (TEM) to problems in space radiation processing. The first problem concerns the role of space radiation processing in controlling the overall fate of Fe sulfides as hosts for sulfur in the ISM. The second problem concerns the known, but as yet poorly quantified, role of space radiation processing in lunar space weathering.

Distribution function of random strains in an elastically anisotropic continuum and defect strengths of T m3 + impurity ions in crystals with zircon structure

NASA Astrophysics Data System (ADS)

Malkin, B. Z.; Abishev, N. M.; Baibekov, E. I.; Pytalev, D. S.; Boldyrev, K. N.; Popova, M. N.; Bettinelli, M.

2017-07-01

We construct a distribution function of the strain-tensor components induced by point defects in an elastically anisotropic continuum, which can be used to account quantitatively for many effects observed in different branches of condensed matter physics. Parameters of the derived six-dimensional generalized Lorentz distribution are expressed through the integrals computed over the array of strains. The distribution functions for the cubic diamond and elpasolite crystals and tetragonal crystals with the zircon and scheelite structures are presented. Our theoretical approach is supported by a successful modeling of specific line shapes of singlet-doublet transitions of the T m3 + ions doped into AB O4 (A =Y , Lu; B =P , V) crystals with zircon structure, observed in high-resolution optical spectra. The values of the defect strengths of impurity T m3 + ions in the oxygen surroundings, obtained as a result of this modeling, can be used in future studies of random strains in different rare-earth oxides.

Mechanistic insights into metal ion activation and operator recognition by the ferric uptake regulator

NASA Astrophysics Data System (ADS)

Deng, Zengqin; Wang, Qing; Liu, Zhao; Zhang, Manfeng; Machado, Ana Carolina Dantas; Chiu, Tsu-Pei; Feng, Chong; Zhang, Qi; Yu, Lin; Qi, Lei; Zheng, Jiangge; Wang, Xu; Huo, Xinmei; Qi, Xiaoxuan; Li, Xiaorong; Wu, Wei; Rohs, Remo; Li, Ying; Chen, Zhongzhou

2015-07-01

Ferric uptake regulator (Fur) plays a key role in the iron homeostasis of prokaryotes, such as bacterial pathogens, but the molecular mechanisms and structural basis of Fur-DNA binding remain incompletely understood. Here, we report high-resolution structures of Magnetospirillum gryphiswaldense MSR-1 Fur in four different states: apo-Fur, holo-Fur, the Fur-feoAB1 operator complex and the Fur-Pseudomonas aeruginosa Fur box complex. Apo-Fur is a transition metal ion-independent dimer whose binding induces profound conformational changes and confers DNA-binding ability. Structural characterization, mutagenesis, biochemistry and in vivo data reveal that Fur recognizes DNA by using a combination of base readout through direct contacts in the major groove and shape readout through recognition of the minor-groove electrostatic potential by lysine. The resulting conformational plasticity enables Fur binding to diverse substrates. Our results provide insights into metal ion activation and substrate recognition by Fur that suggest pathways to engineer magnetotactic bacteria and antipathogenic drugs.

IR spectroscopy of protonation in benzene-water nanoclusters: hydronium, zundel, and eigen at a hydrophobic interface.

PubMed

Cheng, Timothy C; Bandyopadhyay, Biswajit; Mosley, Jonathan D; Duncan, Michael A

2012-08-08

The structure of ions in water at a hydrophobic interface influences important processes throughout chemistry and biology. However, experiments to measure these structures are limited by the distribution of configurations present and the inability to selectively probe the interfacial region. Here, protonated nanoclusters containing benzene and water are produced in the gas phase, size-selected, and investigated with infrared laser spectroscopy. Proton stretch, free OH, and hydrogen-bonding vibrations uniquely define protonation sites and hydrogen-bonding networks. The structures consist of protonated water clusters binding to the hydrophobic interface of neutral benzene via one or more π-hydrogen bonds. Comparison to the spectra of isolated hydronium, zundel, or eigen ions reveals the inductive effects and local ordering induced by the interface. The structures and interactions revealed here represent key features expected for aqueous hydrophobic interfaces.

Ion irradiation induced structural modifications and increase in elastic modulus of silica based thin films

PubMed Central

Shojaee, S. A.; Qi, Y.; Wang, Y. Q.; Mehner, A.; Lucca, D. A.

2017-01-01

Ion irradiation is an alternative to heat treatment for transforming organic-inorganic thin films to a ceramic state. One major shortcoming in previous studies of ion-irradiated films is the assumption that constituent phases in ion-irradiated and heat-treated films are identical and that the ion irradiation effect is limited to changes in composition. In this study, we investigate the effects of ion irradiation on both the composition and structure of constituent phases and use the results to explain the measured elastic modulus of the films. The results indicated that the microstructure of the irradiated films consisted of carbon clusters within a silica matrix. It was found that carbon was present in a non-graphitic sp2-bonded configuration. It was also observed that ion irradiation caused a decrease in the Si-O-Si bond angle of silica, similar to the effects of applied pressure. A phase transformation from tetrahedrally bonded to octahedrally bonded silica was also observed. The results indicated the incorporation of carbon within the silica network. A combination of the decrease in Si-O-Si bond angle and an increase in the carbon incorporation within the silica network was found to be responsible for the increase in the elastic modulus of the films. PMID:28071696

A Sensitivity Enhanced MWCNT/PDMS Tactile Sensor Using Micropillars and Low Energy Ar⁺ Ion Beam Treatment.

PubMed

Azkar Ul Hasan, Syed; Jung, Youngdo; Kim, Seonggi; Jung, Cho-Long; Oh, Sunjong; Kim, Junhee; Lim, Hyuneui

2016-01-12

High sensitive flexible and wearable devices which can detect delicate touches have attracted considerable attentions from researchers for various promising applications. This research was aimed at enhancing the sensitivity of a MWCNT/PDMS piezoresistive tactile sensor through modification of its surface texture in the form of micropillars on MWCNT/PDMS film and subsequent low energy Ar⁺ ion beam treatment of the micropillars. The introduction of straight micropillars on the MWCNT/PDMS surface increased the sensitivity under gentle touch. Low energy ion beam treatment was performed to induce a stiff layer on the exposed surface of the micropillar structured MWCNT/PDMS film. The low energy ion bombardment stabilized the electrical properties of the MWCNT/PDMS surface and tuned the curvature of micropillars according to the treatment conditions. The straight micropillars which were treated by Ar⁺ ion with an incident angle of 0° demonstrated the enhanced sensitivity under normal pressure and the curved micropillars which were treated with Ar⁺ ion with an incident angle of 60° differentiated the direction of an applied shear pressure. The ion beam treatment on micropillar structured MWCNT/PDMS tactile sensors can thus be applied to reliable sensing under gentle touch with directional discrimination.

Ion irradiation induced structural modifications and increase in elastic modulus of silica based thin films

DOE PAGES

Shojaee, S. A.; Qi, Y.; Wang, Y. Q.; ...

2017-01-10

Ion irradiation is an alternative to heat treatment for transforming organic-inorganic thin films to a ceramic state. One major shortcoming in previous studies of ion-irradiated films is the assumption that constituent phases in ion-irradiated and heat-treated films are identical and that the ion irradiation effect is limited to changes in composition. Here, we investigate the effects of ion irradiation on both the composition and structure of constituent phases and use the results to explain the measured elastic modulus of the films. Our results indicated that the microstructure of the irradiated films consisted of carbon clusters within a silica matrix. Itmore » was found that carbon was present in a non-graphitic sp 2-bonded configuration. It was also observed that ion irradiation caused a decrease in the Si-O-Si bond angle of silica, similar to the effects of applied pressure. A phase transformation from tetrahedrally bonded to octahedrally bonded silica was also observed. The results indicated the incorporation of carbon within the silica network. Finally, a combination of the decrease in Si-O-Si bond angle and an increase in the carbon incorporation within the silica network was found to be responsible for the increase in the elastic modulus of the films.« less

Evidence of ion intercalation mediated band structure modification and opto-ionic coupling in lithium niobite

NASA Astrophysics Data System (ADS)

Shank, Joshua C.; Tellekamp, M. Brooks; Doolittle, W. Alan

2015-01-01

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO2), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO2 has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance.

The structural alteration and aggregation propensity of glycated lens crystallins in the presence of calcium: Importance of lens calcium homeostasis in development of diabetic cataracts

NASA Astrophysics Data System (ADS)

ZM, Sara Zafaranchi; Khoshaman, Kazem; Masoudi, Raheleh; Hemmateenejad, Bahram; Yousefi, Reza

2017-01-01

The imbalance of the calcium homeostasis in the lenticular tissues of diabetic patients is an important risk factor for development of cataract diseases. In the current study, the impact of elevated levels of calcium ions were investigated on structure and aggregation propensity of glycated lens crystallins using gel electrophoresis and spectroscopic assessments. The glycated proteins indicated significant resistance against calcium-induced structural insults and aggregation. While, glycated crystallins revealed an increased conformational stability; a slight instability was observed for these proteins upon interaction with calcium ions. Also, in the presence of calcium, the proteolytic pattern of native crystallins was altered and that of glycated protein counterparts remained almost unchanged. According to results of this study it is suggested that the structural alteration of lens crystallins upon glycation may significantly reduce their calcium buffering capacity in eye lenses. Therefore, under chronic hyperglycemia accumulation of this cataractogenic metal ion in the lenticular tissues may subsequently culminate in activation of different pathogenic pathways, leading to development of lens opacity and cataract diseases.

Impact of Ion Bombardment on the Structure and Magnetic Properties of Fe78Si13B9 Amorphous Alloy

NASA Astrophysics Data System (ADS)

Wu, Yingwei; Peng, Kun

2018-06-01

Amorphous Fe78Si13B9 alloy ribbons were bombarded by ion beams with different incident angles ( θ ). The evolution of the microstructure and magnetic properties of ribbons caused by ion beam bombardment was investigated by x-ray diffraction, transmission electron microscope and vibrating sample magnetometer analysis. Low-incident-angle bombardment led to atomic migration in the short range, and high-incident-angle bombardment resulted in the crystallization of amorphous alloys. Ion bombardment induces magnetic anisotropy and affects magnetic properties. The effective magnetic anisotropy was determined by applying the law of approach to saturation, and it increased with the increase of the ion bombardment angle. The introduction of effective magnetic anisotropy will reduce the permeability and increase the relaxation frequency. Excellent high-frequency magnetic properties can be obtained by selecting suitable ion bombardment parameters.

Studies of the beam extraction system of the GTS-LHC electron cyclotron resonance ion source at CERN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Toivanen, V., E-mail: ville.aleksi.toivanen@cern.ch; Küchler, D.

2016-02-15

The 14.5 GHz GTS-LHC Electron Cyclotron Resonance Ion Source (ECRIS) provides multiply charged heavy ion beams for the CERN experimental program. The GTS-LHC beam formation has been studied extensively with lead, argon, and xenon beams with varied beam extraction conditions using the ion optical code IBSimu. The simulation model predicts self-consistently the formation of triangular and hollow beam structures which are often associated with ECRIS ion beams, as well as beam loss patterns which match the observed beam induced markings in the extraction region. These studies provide a better understanding of the properties of the extracted beams and a waymore » to diagnose the extraction system performance and limitations, which is otherwise challenging due to the lack of direct diagnostics in this region and the limited availability of the ion source for development work.« less

Solar Ion Processing of Itokawa Grains: Reconciling Model Predictions with Sample Observations

NASA Technical Reports Server (NTRS)

Christoffersen, Roy; Keller, L. P.

2014-01-01

Analytical TEM observations of Itokawa grains reported to date show complex solar wind ion processing effects in the outer 30-100 nm of pyroxene and olivine grains. The effects include loss of long-range structural order, formation of isolated interval cavities or "bubbles", and other nanoscale compositional/microstructural variations. None of the effects so far described have, however, included complete ion-induced amorphization. To link the array of observed relationships to grain surface exposure times, we have adapted our previous numerical model for progressive solar ion processing effects in lunar regolith grains to the Itokawa samples. The model uses SRIM ion collision damage and implantation calculations within a framework of a constant-deposited-energy model for amorphization. Inputs include experimentally-measured amorphization fluences, a Pi steradian variable ion incidence geometry required for a rotating asteroid, and a numerical flux-versus-velocity solar wind spectrum.

In-Situ atomic force microscopic observation of ion beam bombarded plant cell envelopes

NASA Astrophysics Data System (ADS)

Sangyuenyongpipat, S.; Yu, L. D.; Brown, I. G.; Seprom, C.; Vilaithong, T.

2007-04-01

A program in ion beam bioengineering has been established at Chiang Mai University (CMU), Thailand, and ion beam induced transfer of plasmid DNA molecules into bacterial cells (Escherichia coli) has been demonstrated. However, a good understanding of the fundamental physical processes involved is lacking. In parallel work, onion skin cells have been bombarded with Ar+ ions at energy 25 keV and fluence1-2 × 1015 ions/cm2, revealing the formation of microcrater-like structures on the cell wall that could serve as channels for the transfer of large macromolecules into the cell interior. An in-situ atomic force microscope (AFM) system has been designed and installed in the CMU bio-implantation facility as a tool for the observation of these microcraters during ion beam bombardment. Here we describe some of the features of the in-situ AFM and outline some of the related work.

The effects on γ-LiAlO2 induced by nuclear energy losses during Ga ions implantation

NASA Astrophysics Data System (ADS)

Zhang, Jing; Song, Hong-Lian; Qiao, Mei; Yu, Xiao-Fei; Wang, Tie-Jun; Wang, Xue-Lin

2017-09-01

To explore the evolution of γ-LiAlO2 under ion irradiation at low energy, we implanted Ga ions of 30, 80 and 150 keV at fluences of 1 × 1014 and 1 × 1015 ions/cm2 in z-cut γ-LiAlO2 samples, respectively. The implantation resulted in damage regions dominated by nuclear energy losses at depth of 232 Å, 514 Å, and 911 Å beneath the surface, respectively, which was simulated by the Stopping and Range of Ions in Matter program. The irradiated γ-LiAlO2 were characterized with atomic force microscope, Raman spectroscopy, X-ray diffraction and Rutherford backscattering in a channeling mode for morphology evolution, structure information and damage profiles. The interesting and partly abnormal results showed the various behaviors in modification of surface by Ga ions implantation.

Secondary ion emission from Ti, V, Cu, Ag and Au surfaces under KeV Cs + irradiation

NASA Astrophysics Data System (ADS)

van der Heide, P. A. W.

2005-02-01

Low energy mono-atomic singly charged secondary ion emissions from Ti, V, Cu, Ag and Au substrates during the initial stages of sputtering with Cs + primary ions have been studied. With the exception of the Ag - secondary ions, all exhibited exponential like correlations with the Cs induced work function changes. This, along with the lack of variations in the valence band structure around the Fermi edge, is consistent with resonance charge transfer to/from states located at the Fermi edge. The insensitivity of Ag - to work function appears to stem from the dominance of a separate ion formation process, namely charge transfer into vacant 4d states in the sputtered population, which themselves appear to be produced through collective oscillations. A similar excitation-mediated process involving different levels also appears to be active in the formation of other negatively charged transition metal ions, albeit to a much lesser degree.

Effects of neutron and gamma radiation on lithium-ion batteries

NASA Astrophysics Data System (ADS)

Qiu, Jie; He, Dandan; Sun, Mingzhai; Li, Shimeng; Wen, Cun; Hattrick-Simpers, Jason; Zheng, Yuan F.; Cao, Lei

2015-02-01

Radiation induced deterioration in the performance of lithium-ion (Li-ion) batteries can result in functional failures of electronic devices in modern electronic systems. The stability of the Li-ion battery under a radiation environment is of crucial importance. In this work, the surface morphology of the cathode material of a commercial Li-ion battery before and after neutron and gamma ray irradiation was characterized by atomic force microscopy (AFM). We found growth in the particle size of the cathode material in the range of 36-45% as a result of the irradiation. In addition, X-ray diffraction (XRD) patterns revealed a disordering of the crystal structure occurring in the post-irradiation sample. All of these led to a 8.4% capacity loss of the battery for the maximum received irradiation dose (2.744 Mrad) at post-irradiation. The effects of the radiation on the Li-ion battery are discussed in this paper.

Studies of the beam extraction system of the GTS-LHC electron cyclotron resonance ion source at CERN.

PubMed

Toivanen, V; Küchler, D

2016-02-01

The 14.5 GHz GTS-LHC Electron Cyclotron Resonance Ion Source (ECRIS) provides multiply charged heavy ion beams for the CERN experimental program. The GTS-LHC beam formation has been studied extensively with lead, argon, and xenon beams with varied beam extraction conditions using the ion optical code IBSimu. The simulation model predicts self-consistently the formation of triangular and hollow beam structures which are often associated with ECRIS ion beams, as well as beam loss patterns which match the observed beam induced markings in the extraction region. These studies provide a better understanding of the properties of the extracted beams and a way to diagnose the extraction system performance and limitations, which is otherwise challenging due to the lack of direct diagnostics in this region and the limited availability of the ion source for development work.

Copper Ion Beam Irradiation-Induced Effects on Structural, Morphological and Optical Properties of Tin Dioxide Nanowires

NASA Astrophysics Data System (ADS)

A. Khan, M.; Qayyum, A.; I., Ahmed; T., Iqbal; A. Khan, A.; Waleed, R.; Mohuddin, B.; Malik, M.

2016-07-01

Not Available Supported by the Department of Physics, the University of AJK, High Tech. Centralized Instrumentation Lab, the University of AJK, Pakistan and the Experimental Physics Division, and the National Center for Physics, Islamabad Pakistan.

Kinetics of Electrons from Plasma Discharge in a Latent Track Region Induced by Swift Heavy ION Irradiation

NASA Astrophysics Data System (ADS)

Minárik, Stanislav

2015-08-01

While passing swift heavy ion through a material structure, it produces a region of radiation affected material which is known as a "latent track". Scattering motions of electrons interacting with a swift heavy ion are dominant in the latent track region. These phenomena include the electron impurity and phonon scattering processes modified by the interaction with the ion projectile as well as the Coulomb scattering between two electrons. In this paper, we provide detailed derivation of a 3D Boltzmann scattering equation for the description of the relative scattering motion of such electrons. Phase-space distribution function for this non-equilibrioum system of scattering electrons can be found by the solution of mentioned equation.

A mass spectrometric study of gaseous H4PO+3 and H2PO-3 ions

NASA Astrophysics Data System (ADS)

de Petris, Giulia; Occhiucci, Giorgio; Pepi, Federico

1994-09-01

H4PO+3 ions have been generated in a mass spectrometer by proton-transfer to H3PO3 from different Brønsted acids. The proton affinity of H3PO3 has been estimated by bracketing and kinetic methods to be 198.6 ± 2 kcal mol-1. Gaseous H4PO+3 ions have been structurally assessed by metastable ion kinetic energy (MIKE) and collisionally induced dissociation (CID) mass spectrometry leading to the detection of a single isomeric species. The chemistry of H2PO-3 is characterized by facile addition-elimination reactions leading to formation of polyanions. Species containing up to six P atoms have been detected.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohshimo, Keijiro; Institute for Excellence in Higher Education, Tohoku University, 41 Kawauchi, Aoba-ku, Sendai 980-8576; Norimasa, Naoya

Geometrical structures of titanium oxide cluster cations and anions have been investigated by ion mobility mass spectrometry and quantum chemical calculations based on density functional theory. Stable cluster compositions with respect to collision induced dissociation were also determined by changing ion injection energy to an ion drift cell for mobility measurements. The Ti{sub n}O{sub 2n−1}{sup +} cations and Ti{sub n}O{sub 2n}{sup −} anions were predominantly observed at high injection energies, in addition to Ti{sub n}O{sub 2n}{sup +} for cations and Ti{sub n}O{sub 2n+1}{sup −} for anions. Collision cross sections of Ti{sub n}O{sub 2n}{sup +} and Ti{sub n}O{sub 2n+1}{sup −} formore » n = 1-7, determined by ion mobility mass spectrometry, were compared with those obtained theoretically as orientation-averaged cross sections for the optimized structures by quantum chemical calculations. All of the geometrical structures thus assigned have three-dimensional structures, which are in marked contrast with other oxides of late transition metals. One-oxygen atom dissociation processes from Ti{sub n}O{sub 2n}{sup +} and Ti{sub n}O{sub 2n+1}{sup −} by collisions were also explained by analysis of spin density distributions.« less

Ion beams provided by small accelerators for material synthesis and characterization

NASA Astrophysics Data System (ADS)

Mackova, Anna; Havranek, Vladimir

2017-06-01

The compact, multipurpose electrostatic tandem accelerators are extensively used for production of ion beams with energies in the range from 400 keV to 24 MeV of almost all elements of the periodic system for the trace element analysis by means of nuclear analytical methods. The ion beams produced by small accelerators have a broad application, mainly for material characterization (Rutherford Back-Scattering spectrometry, Particle Induced X ray Emission analysis, Nuclear Reaction Analysis and Ion-Microprobe with 1 μm lateral resolution among others) and for high-energy implantation. Material research belongs to traditionally progressive fields of technology. Due to the continuous miniaturization, the underlying structures are far beyond the analytical limits of the most conventional methods. Ion Beam Analysis (IBA) techniques provide this possibility as they use probes of similar or much smaller dimensions (particles, radiation). Ion beams can be used for the synthesis of new progressive functional nanomaterials for optics, electronics and other applications. Ion beams are extensively used in studies of the fundamental energetic ion interaction with matter as well as in the novel nanostructure synthesis using ion beam irradiation in various amorphous and crystalline materials in order to get structures with extraordinary functional properties. IBA methods serve for investigation of materials coming from material research, industry, micro- and nano-technology, electronics, optics and laser technology, chemical, biological and environmental investigation in general. Main research directions in laboratories employing small accelerators are also the preparation and characterization of micro- and nano-structured materials which are of interest for basic and oriented research in material science, and various studies of biological, geological, environmental and cultural heritage artefacts are provided too.

Reentrant behaviors in the phase diagram of spin-1 planar ferromagnet with single-ion anisotropy

NASA Astrophysics Data System (ADS)

Rabuffo, I.; De Cesare, L.; Caramico D'Auria, A.; Mercaldo, M. T.

2018-05-01

We used the two-time Green function framework to investigate the role played by the easy-axis single-ion anisotropy on the phase diagram of (d > 2)-dimensional spin-1planar ferromagnets, which exhibit a magnetic field induced quantum phase transition. We tackled the problem using two different kind of approximations: the Anderson-Callen decoupling scheme and the Devlin approach. In the latter scheme, the exchange anisotropy terms in the equations of motion are treated at the Tyablikov decoupling level while the crystal field anisotropy contribution is handled exactly. The emerging key result is a reentrant structure of the phase diagram close to the quantum critical point, for certain values of the single-ion anisotropy parameter. We compare the results obtained within the two approximation schemes. In particular, we recover the same qualitative behavior. We show the phase diagram, close to the field-induced quantum critical point and the behavior of the susceptibility for different values of the single-ion anisotropy parameter, enhancing the differences between the two different scenarios (i.e. with and without reentrant behavior).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnard, John J.; Schenkel, Thomas

Intense, pulsed ion beams locally heat materials and deliver dense electronic excitations that can induce material modifications and phase transitions. Material properties can potentially be stabilized by rapid quenching. Pulsed ion beams with pulse lengths of order ns have recently become available for materials processing. Here, we optimize mask geometries for local modification of materials by intense ion pulses. The goal is to rapidly excite targets volumetrically to the point where a phase transition or local lattice reconstruction is induced followed by rapid cooling that stabilizes desired material's properties fast enough before the target is altered or damaged by, e.g.,more » hydrodynamic expansion. By using a mask, the longitudinal dimension can be large compared to the transverse dimension, allowing the possibility of rapid transverse cooling. We performed HYDRA simulations that calculate peak temperatures for a series of excitation conditions and cooling rates of silicon targets with micro-structured masks and compare these to a simple analytical model. In conclusion, the model gives scaling laws that can guide the design of targets over a wide range of pulsed ion beam parameters.« less

Gas-phase structure and fragmentation pathways of singly protonated peptides with N-terminal arginine.

PubMed

Bythell, Benjamin J; Csonka, István P; Suhai, Sándor; Barofsky, Douglas F; Paizs, Béla

2010-11-25

The gas-phase structures and fragmentation pathways of the singly protonated peptide arginylglycylaspartic acid (RGD) are investigated by means of collision-induced-dissociation (CID) and detailed molecular mechanics and density functional theory (DFT) calculations. It is demonstrated that despite the ionizing proton being strongly sequestered at the guanidine group, protonated RGD can easily be fragmented on charge directed fragmentation pathways. This is due to facile mobilization of the C-terminal or aspartic acid COOH protons thereby generating salt-bridge (SB) stabilized structures. These SB intermediates can directly fragment to generate b(2) ions or facilely rearrange to form anhydrides from which both b(2) and b(2)+H(2)O fragments can be formed. The salt-bridge stabilized and anhydride transition structures (TSs) necessary to form b(2) and b(2)+H(2)O are much lower in energy than their traditional charge solvated counterparts. These mechanisms provide compelling evidence of the role of SB and anhydride structures in protonated peptide fragmentation which complements and supports our recent findings for tryptic systems (Bythell, B. J.; Suhai, S.; Somogyi, A.; Paizs, B. J. Am. Chem. Soc. 2009, 131, 14057-14065.). In addition to these findings we also report on the mechanisms for the formation of the b(1) ion, neutral loss (H(2)O, NH(3), guanidine) fragment ions, and the d(3) ion.

Ion-Exchange-Induced Selective Etching for the Synthesis of Amino-Functionalized Hollow Mesoporous Silica for Elevated-High-Temperature Fuel Cells.

PubMed

Zhang, Jin; Liu, Jian; Lu, Shanfu; Zhu, Haijin; Aili, David; De Marco, Roland; Xiang, Yan; Forsyth, Maria; Li, Qingfeng; Jiang, San Ping

2017-09-20

As differentiated from conventional synthetic processes, amino-functionalized hollow mesoporous silica (NH 2 -HMS) has been synthesized using a new and facile strategy of ion-exchange-induced selective etching of amino-functionalized mesoporous silica (NH 2 -meso-silica) by an alkaline solution. Nuclear magnetic resonance (NMR) spectroscopy and in situ time-resolved small-angle X-ray scattering (SAXS) reveal that ion-exchange-induced selective etching arises from the gradient distribution of OH - in the NH 2 -meso-silica nanospheres. Moreover, the ion-exchange-induced selective etching mechanism is verified through a successful synthesis of hollow mesoporous silica. After infiltration with phosphotungstic acid (PWA), PWA-NH 2 -HMS nanoparticles are dispersed in the poly(ether sulfone)-polyvinylpyrrolidone (PES-PVP) matrix, forming a hybrid PWA-NH 2 -HMS/PES-PVP nanocomposite membrane. The resultant nanocomposite membrane with an optimum loading of 10 wt % of PWA-NH 2 -HMS showed an enhanced proton conductivity of 0.175 S cm -1 and peak power density of 420 mW cm -2 at 180 °C under anhydrous conditions. Excellent durability of the hybrid composite membrane fuel cell has been demonstrated at 200 °C. The results of this study demonstrated the potential of the facile synthetic strategy in the fabrication of NH 2 -HMS with controlled mesoporous structure for application in nanocomposite membranes as a technology platform for elevated-temperature proton exchange membrane fuel cells.

Identification of ion-pair structures in solution by vibrational stark effects

DOE PAGES

Hack, John; Mani, Tomoyasu; Grills, David C.; ...

2016-01-25

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N)more » infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

Identification of ion-pair structures in solution by vibrational stark effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hack, John; Mani, Tomoyasu; Grills, David C.

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N)more » infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

Local Structures Around Co Atoms in Wurtzite ZnO Nano-Composites Probed by Fluorescence XAFS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi Tongfei; National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029; Liu Wenhan

2007-02-02

The local structures around Co ions in the Zn1-xCoxO nano-composites prepared by the sol-gel method have been investigated by fluorescence X-ray absorption fine structure (XAFS) technique. The results indicate that for dilute Co-doped ZnO (x=0.02, 0.05), the Co2+ ions are incorporated into the ZnO lattice, and are located at the position of the substitutional Zn2+ ions. As the Co content increases to 0.10 or higher, only part of the Co ions enter the lattice of the wurtzite and the others exist in the form of a Co3O4 phase whose content increases with the doped Co concentration. In the substitutional Zn0.98Co0.02Omore » sample, the bond length of the first shell RCo-O and the second shell RCo-Zn is smaller than the second shell Zn-Zn distance in ZnO by about 0.01{approx}0.02 A. These results imply that only small local lattice deformation is induced by dilute Co2+ substituting into the Zn2+ sites.« less

Calcium ion binding properties and the effect of phosphorylation on the intrinsically disordered Starmaker protein.

PubMed

Wojtas, Magdalena; Hołubowicz, Rafał; Poznar, Monika; Maciejewska, Marta; Ożyhar, Andrzej; Dobryszycki, Piotr

2015-10-27

Starmaker (Stm) is an intrinsically disordered protein (IDP) involved in otolith biomineralization in Danio rerio. Stm controls calcium carbonate crystal formation in vivo and in vitro. Phosphorylation of Stm affects its biomineralization properties. This study examined the effects of calcium ions and phosphorylation on the structure of Stm. We have shown that CK2 kinase phosphorylates 25 or 26 residues in Stm. Furthermore, we have demonstrated that Stm's affinity for calcium binding is dependent on its phosphorylation state. Phosphorylated Stm (StmP) has an estimated 30 ± 1 calcium binding sites per protein molecule with a dissociation constant (KD) of 61 ± 4 μM, while the unphosphorylated protein has 28 ± 3 sites and a KD of 210 ± 22 μM. Calcium ion binding induces a compaction of the Stm molecule, causing a significant decrease in its hydrodynamic radius and the formation of a secondary structure. The screening effect of Na(+) ions on calcium binding was also observed. Analysis of the hydrodynamic properties of Stm and StmP showed that Stm and StmP molecules adopt the structure of native coil-like proteins.

Concurrent segregation and erosion effects in medium-energy iron beam patterning of silicon surfaces

NASA Astrophysics Data System (ADS)

Redondo-Cubero, A.; Lorenz, K.; Palomares, F. J.; Muñoz, A.; Castro, M.; Muñoz-García, J.; Cuerno, R.; Vázquez, L.

2018-07-01

We have bombarded crystalline silicon targets with a 40 keV Fe+ ion beam at different incidence angles. The resulting surfaces have been characterized by atomic force, current-sensing and magnetic force microscopies, scanning electron microscopy, and x-ray photoelectron spectroscopy. We have found that there is a threshold angle smaller than 40° for the formation of ripple patterns, which is definitely lower than those frequently reported for noble gas ion beams. We compare our observations with estimates of the value of the critical angle and of additional basic properties of the patterning process, which are based on a continuum model whose parameters are obtained from binary collision simulations. We have further studied experimentally the ripple structures and measured how the surface slopes change with the ion incidence angle. We explore in particular detail the fluence dependence of the pattern for an incidence angle value (40°) close to the threshold. Initially, rimmed holes appear randomly scattered on the surface, which evolve into large, bug-like structures. Further increasing the ion fluence induces a smooth, rippled background morphology. By means of microscopy techniques, a correlation between the morphology of these structures and their metal content can be unambiguously established.

Kinetic Aspects of Surfactant-Induced Structural Changes of Proteins - Unsolved Problems of Two-State Model for Protein Denaturation -.

PubMed

Takeda, Kunio; Moriyama, Yoshiko

2015-01-01

The kinetic mechanism of surfactant-induced protein denaturation is discussed on the basis of not only stopped-flow kinetic data but also the changes of protein helicities caused by the surfactants and the discontinuous mobility changes of surfactant-protein complexes. For example, the α-helical structures of bovine serum albumin (BSA) are partially disrupted due to the addition of sodium dodecyl sulfate (SDS). Formation of SDS-BSA complex can lead to only four complex types with specific mobilities depending on the surfactant concentration. On the other hand, the apparent rate constant of the structural change of BSA increases with an increase of SDS concentration, indicating that the rate of the structural change becomes fast as the degree of the change increases. When a certain amount of surfactant ions bind to proteins, their native structures transform directly to particular structures without passing through intermediate stages that might be induced due to the binding of fewer amounts of the surfactant ions. Furthermore, this review brings up a question about two-state and three-state models, N⇌D and N⇌D'⇌D (N: native state, D: denatured sate, D': intermediate between N and D), which have been often adopted without hesitation in discussion on general denaturations of proteins. First of all, doubtful is whether any equilibrium relationship exists in such denaturation reactions. It cannot be disregarded that the D states in these models differ depending on the changes of intensities of the denaturing factors. The authors emphasize that the denaturations or the structural changes of proteins should be discussed assuming one-way reaction models with no backward processes rather than assuming the reversible two-state reaction models or similar modified reaction models.

Excitation-Energy Transfer Paths from Tryptophans to Coordinated Copper Ions in Engineered Azurins: a Source of Observables for Monitoring Protein Structural Changes

NASA Astrophysics Data System (ADS)

Di Rocco, Giulia; Bernini, Fabrizio; Borsari, Marco; Martinelli, Ilaria; Bortolotti, Carlo Augusto; Battistuzzi, Gianantonio; Ranieri, Antonio; Caselli, Monica; Sola, Marco; Ponterini, Glauco

2016-09-01

The intrinsic fluorescence of recombinant proteins offers a powerful tool to detect and characterize structural changes induced by chemical or biological stimuli. We show that metal-ion binding to a hexahistidine tail can significantly broaden the range of such structurally sensitive fluorescence observables. Bipositive metal-ions as Cu2+, Ni2+ and Zn2+ bind 6xHis-tag azurin and its 6xHis-tagged R129W and W48A-R129W mutants with good efficiency and, thereby, quench their intrinsic fluorescence. Due to a much more favourable spectral overlap, the 6xHis-tag/Cu2+ complex(es) are the most efficient quenchers of both W48 and W129 emissions. Based on simple Förster-type dependence of energy-transfer efficiency on donor/acceptor distance, we can trace several excitation-energy transfer paths across the protein structure. Unexpected lifetime components in the azurin 6xHis-tag/Cu2+ complex emission decays reveal underneath complexity in the conformational landscape of these systems. The new tryptophan emission quenching paths provide additional signals for detecting and identifying protein structural changes.

Recrystallization-Induced Surface Cracks of Carbon Ions Irradiated 6H-SiC after Annealing.

PubMed

Ye, Chao; Ran, Guang; Zhou, Wei; Shen, Qiang; Feng, Qijie; Lin, Jianxin

2017-10-25

Single crystal 6H-SiC wafers with 4° off-axis [0001] orientation were irradiated with carbon ions and then annealed at 900 °C for different time periods. The microstructure and surface morphology of these samples were investigated by grazing incidence X-ray diffraction (GIXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Ion irradiation induced SiC amorphization, but the surface was smooth and did not have special structures. During the annealing process, the amorphous SiC was recrystallized to form columnar crystals that had a large amount of twin structures. The longer the annealing time was, the greater the amount of recrystallized SiC would be. The recrystallization volume fraction was accorded with the law of the Johnson-Mehl-Avrami equation. The surface morphology consisted of tiny pieces with an average width of approximately 30 nm in the annealed SiC. The volume shrinkage of irradiated SiC layer and the anisotropy of newly born crystals during annealing process produced internal stress and then induced not only a large number of dislocation walls in the non-irradiated layer but also the initiation and propagation of the cracks. The direction of dislocation walls was perpendicular to the growth direction of the columnar crystal. The longer the annealing time was, the larger the length and width of the formed crack would be. A quantitative model of the crack growth was provided to calculate the length and width of the cracks at a given annealing time.

Nickel nanowires mesh fabricated by ion beam irradiation-induced nanoscale welding for transparent conducting electrodes

NASA Astrophysics Data System (ADS)

Honey, S.; Ahmad, I.; Madhuku, M.; Naseem, S.; Maaza, M.; Kennedy, J. V.

2017-07-01

In this report, random nickel nanowires (Ni-NWs) meshes are fabricated by ions beam irradiation-induced nanoscale welding of NWs on intersecting positions. Ni-NWs are exposed to beam of 50 KeV Argon (Ar+) ions at various fluencies in the range ~1015 ions cm-2 to 1016 ions cm-2 at room temperature. Ni-NWs are welded due to accumulation of Ar+ ions beam irradiation-induced sputtered atoms on crossing positions. Ar+ ions irradiated Ni-NWs meshes are optically transparent and optical transparency is enhanced with increase in beam fluence of Ar+ ions. Ar+ ions beam irradiation-induced welded and optically transparent mesh is then exposed to 2.75 MeV hydrogen (H+) ions at fluencies 1  ×  1015 ions cm-2, 3  ×  1015 ions cm-2 and 1  ×  1016 ions cm-2 at room temperature. MeV H+ ions irradiation-induced local heat cause melting and fusion of NWs on intersecting points and eventually lead to reduce contact resistance between Ni-NWs. Electrical conductivity is enhanced with increase in beam fluence of H+ ions. These welded highly transparent and electrically conductive Ni-NWs meshes can be employed as transparent conducting electrodes in optoelectronic devices.

Pressure induced structural phase transition in IB transition metal nitrides compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soni, Shubhangi; Kaurav, Netram, E-mail: netramkaurav@yahoo.co.uk; Jain, A.

2015-06-24

Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbormore » ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.« less

Comparing solvophobic and multivalent induced collapse in polyelectrolyte brushes

DOE PAGES

Jackson, Nicholas E.; Brettmann, Blair K.; Vishwanath, Venkatram; ...

2017-02-03

Here, coarse-grained molecular dynamics enhanced by free-energy sampling methods is used to examine the roles of solvophobicity and multivalent salts on polyelectrolyte brush collapse. Specifically, we demonstrate that while ostensibly similar, solvophobic collapsed brushes and multivalent-ion collapsed brushes exhibit distinct mechanistic and structural features. Notably, multivalent-induced heterogeneous brush collapse is observed under good solvent polymer backbone conditions, demonstrating that the mechanism of multivalent collapse is not contingent upon a solvophobic backbone. Umbrella sampling of the potential of mean-force (PMF) between two individual brush strands confirms this analysis, revealing starkly different PMFs under solvophobic and multivalent conditions, suggesting the role ofmore » multivalent “bridging” as the discriminating feature in trivalent collapse. Structurally, multivalent ions show a propensity for nucleating order within collapsed brushes, whereas poor-solvent collapsed brushes are more disordered; this difference is traced to the existence of a metastable PMF minimum for poor solvent conditions, and a global PMF minimum for trivalent systems, under experimentally relevant conditions.« less

Comparing solvophobic and multivalent induced collapse in polyelectrolyte brushes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jackson, Nicholas E.; Brettmann, Blair K.; Vishwanath, Venkatram

Here, coarse-grained molecular dynamics enhanced by free-energy sampling methods is used to examine the roles of solvophobicity and multivalent salts on polyelectrolyte brush collapse. Specifically, we demonstrate that while ostensibly similar, solvophobic collapsed brushes and multivalent-ion collapsed brushes exhibit distinct mechanistic and structural features. Notably, multivalent-induced heterogeneous brush collapse is observed under good solvent polymer backbone conditions, demonstrating that the mechanism of multivalent collapse is not contingent upon a solvophobic backbone. Umbrella sampling of the potential of mean-force (PMF) between two individual brush strands confirms this analysis, revealing starkly different PMFs under solvophobic and multivalent conditions, suggesting the role ofmore » multivalent “bridging” as the discriminating feature in trivalent collapse. Structurally, multivalent ions show a propensity for nucleating order within collapsed brushes, whereas poor-solvent collapsed brushes are more disordered; this difference is traced to the existence of a metastable PMF minimum for poor solvent conditions, and a global PMF minimum for trivalent systems, under experimentally relevant conditions.« less

Crystal structure and dynamics of a lipid-induced potential desensitized-state of a pentameric ligand-gated channel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basak, Sandip; Schmandt, Nicolaus; Gicheru, Yvonne

Desensitization in pentameric ligand-gated ion channels plays an important role in regulating neuronal excitability. Here, we show that docosahexaenoic acid (DHA), a key ω-3 polyunsaturated fatty acid in synaptic membranes, enhances the agonist-induced transition to the desensitized state in the prokaryotic channel GLIC. We determined a 3.25 Å crystal structure of the GLIC-DHA complex in a potentially desensitized conformation. The DHA molecule is bound at the channel-periphery near the M4 helix and exerts a long-range allosteric effect on the pore across domain-interfaces. In this previously unobserved conformation, the extracellular-half of the pore-lining M2 is splayed open, reminiscent of the openmore » conformation, while the intracellular-half is constricted, leading to a loss of both water and permeant ions. These findings, in combination with spin-labeling/EPR spectroscopic measurements in reconstituted-membranes, provide novel mechanistic details of desensitization in pentameric channels.« less

Finding the rhythm of sudden cardiac death: new opportunities using induced pluripotent stem cell-derived cardiomyocytes.

PubMed

Sallam, Karim; Li, Yingxin; Sager, Philip T; Houser, Steven R; Wu, Joseph C

2015-06-05

Sudden cardiac death is a common cause of death in patients with structural heart disease, genetic mutations, or acquired disorders affecting cardiac ion channels. A wide range of platforms exist to model and study disorders associated with sudden cardiac death. Human clinical studies are cumbersome and are thwarted by the extent of investigation that can be performed on human subjects. Animal models are limited by their degree of homology to human cardiac electrophysiology, including ion channel expression. Most commonly used cellular models are cellular transfection models, which are able to mimic the expression of a single-ion channel offering incomplete insight into changes of the action potential profile. Induced pluripotent stem cell-derived cardiomyocytes resemble, but are not identical, adult human cardiomyocytes and provide a new platform for studying arrhythmic disorders leading to sudden cardiac death. A variety of platforms exist to phenotype cellular models, including conventional and automated patch clamp, multielectrode array, and computational modeling. Induced pluripotent stem cell-derived cardiomyocytes have been used to study long QT syndrome, catecholaminergic polymorphic ventricular tachycardia, hypertrophic cardiomyopathy, and other hereditary cardiac disorders. Although induced pluripotent stem cell-derived cardiomyocytes are distinct from adult cardiomyocytes, they provide a robust platform to advance the science and clinical care of sudden cardiac death. © 2015 American Heart Association, Inc.

The effect of group IIIA metal ion dopants on the photocatalytic activities of nanocrystalline Sr0.25H1.5Ta2O6·H2O.

PubMed

Liang, Shijing; Zhu, Shuying; Zhu, Jia; Chen, Yan; Zhang, Yongfan; Wu, Ling

2012-01-21

A series of group IIIA metal ion electron acceptors doped into Sr(0.25)H(1.5)Ta(2)O(6)·H(2)O (HST) samples have been prepared by an impregnation and calcination method for the first time. The samples are characterized by XRD, TEM, DRS and XPS. The variations in the electronic structure and photoelectric response after metal ion doping are investigated by theoretical calculations and photocurrent experiments, respectively. Results show that the metal ions can be efficiently incorporated into the HST crystal structure, which is reflected in the lattice contraction. Meanwhile, the photoabsorption edges of the metal-doped HST samples are red shifted to a longer wavelength. Taking into account the ionic radii and electronegativities of the dopants, as well as the XRD and XPS results, it is concluded that Ta(5+) ions may be partially substituted by the Al(3+) and Ga(3+) ions in the framework, while In(3+) ions are the favourable substitutes for Sr(2+) sites in the cavity. The first-principles DFT calculations confirm that the variation of the band structure is sensitive to the type of group IIIA metal ion. Introducing the dopant only at the Ta site induces an obvious variation in the band structure and the band gap becomes narrow. Meanwhile, an ''extra step'' appeared in the band gap, which can trap photogenerated electrons from the valance band (VB) and could enhance the charge mobility and the photocurrent. For the photocatalytic degradation of methyl orange in an aqueous solution and in benzene in the gas phase, the doped samples show superior photocatalytic activities compared with both undoped samples and TiO(2). The enhanced photocatalytic activities can be well explained by their electronic structure, photoabsorption performance, photoelectric response, and the concentration of the active species. Due to the fact that Ga ion doping can create an acceptor impurity level and change the electronic band, efficiently narrowing the band gap, the Ga-doped sample shows the highest photocatalytic activity.

Ion beam induced defects in solids studied by optical techniques

NASA Astrophysics Data System (ADS)

Comins, J. D.; Amolo, G. O.; Derry, T. E.; Connell, S. H.; Erasmus, R. M.; Witcomb, M. J.

2009-08-01

Optical methods can provide important insights into the mechanisms and consequences of ion beam interactions with solids. This is illustrated by four distinctly different systems. X- and Y-cut LiNbO 3 crystals implanted with 8 MeV Au 3+ ions with a fluence of 1 × 10 17 ions/cm 2 result in gold nanoparticle formation during high temperature annealing. Optical extinction curves simulated by the Mie theory provide the average nanoparticle sizes. TEM studies are in reasonable agreement and confirm a near-spherical nanoparticle shape but with surface facets. Large temperature differences in the nanoparticle creation in the X- and Y-cut crystals are explained by recrystallisation of the initially amorphised regions so as to recreate the prior crystal structure and to result in anisotropic diffusion of the implanted gold. Defect formation in alkali halides using ion beam irradiation has provided new information. Radiation-hard CsI crystals bombarded with 1 MeV protons at 300 K successfully produce F-type centres and V-centres having the I3- structure as identified by optical absorption and Raman studies. The results are discussed in relation to the formation of interstitial iodine aggregates of various types in alkali iodides. Depth profiling of I3- and I5- aggregates created in RbI bombarded with 13.6 MeV/A argon ions at 300 K is discussed. The recrystallisation of an amorphous silicon layer created in crystalline silicon bombarded with 100 keV carbon ions with a fluence of 5 × 10 17 ions/cm 2 during subsequent high temperature annealing is studied by Raman and Brillouin light scattering. Irradiation of tin-doped indium oxide (ITO) films with 1 MeV protons with fluences from 1 × 10 15 to 250 × 10 15 ions/cm -2 induces visible darkening over a broad spectral region that shows three stages of development. This is attributed to the formation of defect clusters by a model of defect growth and also high fluence optical absorption studies. X-ray diffraction studies show evidence of a strained lattice after the proton bombardment and recovery after long period storage. The effects are attributed to the annealing of the defects produced.

Hollow SnO2 nanospheres with oxygen vacancies entrapped by a N-doped graphene network as robust anode materials for lithium-ion batteries.

PubMed

Wu, Naiteng; Du, Wuzhou; Gao, Xu; Zhao, Liang; Liu, Guilong; Liu, Xianming; Wu, Hao; He, Yan-Bing

2018-06-21

The practical application of tin dioxide (SnO2) in lithium-ion batteries has been greatly hindered by its large volumetric expansion and low conductivity. Thus, a rational design of the size, geometry and the pore structure of SnO2-based nanomaterials is still a dire demand. To this end, herein we report an effective approach for engineering hollow-structured SnO2 nanospheres with adequate surface oxygen vacancies simultaneously wrapped by a nitrogen-doped graphene network (SnO2-x/N-rGO) through an electrostatic adsorption-induced self-assembly together with a thermal reduction process. The close electrostatic attraction achieved a tight and uniform combination of positively charged SnO2 nanospheres with negatively charged graphene oxide (GO), which can alleviate the aggregation and volume expansion of the entrapped SnO2 nanospheres. Subsequent thermal treatment not only ensures a significant reduction of the GO sheets accompanying nitrogen-doping, but also induces the generation of oxygen vacancies on the surface of the SnO2 hollow nanospheres, together building up a long-range and bicontinuous transfer channel for rapid electron and ion transport. Because of these structural merits, the as-built SnO2-x/N-rGO composite used as the anode material exhibits excellent robust cycling stability (∼912 mA h g-1 after 500 cycles at 0.5 A g-1 and 652 mA h g-1 after 200 cycles at 1 A g-1) and superior rate capability (309 mA h g-1 at 10 A g-1). This facile fabrication strategy may pave the way for the construction of high performance SnO2-based anode materials for potential application in advanced lithium-ion batteries.

Global structure of forked DNA in solution revealed by high-resolution single-molecule FRET.

PubMed

Sabir, Tara; Schröder, Gunnar F; Toulmin, Anita; McGlynn, Peter; Magennis, Steven W

2011-02-09

Branched DNA structures play critical roles in DNA replication, repair, and recombination in addition to being key building blocks for DNA nanotechnology. Here we combine single-molecule multiparameter fluorescence detection and molecular dynamics simulations to give a general approach to global structure determination of branched DNA in solution. We reveal an open, planar structure of a forked DNA molecule with three duplex arms and demonstrate an ion-induced conformational change. This structure will serve as a benchmark for DNA-protein interaction studies.

Probing structural features of Alzheimer's amyloid-β pores in bilayers using site-specific amino acid substitutions.

PubMed

Capone, Ricardo; Jang, Hyunbum; Kotler, Samuel A; Kagan, Bruce L; Nussinov, Ruth; Lal, Ratnesh

2012-01-24

A current hypothesis for the pathology of Alzheimer's disease (AD) proposes that amyloid-β (Aβ) peptides induce uncontrolled, neurotoxic ion flux across cellular membranes. The mechanism of ion flux is not fully understood because no experiment-based Aβ channel structures at atomic resolution are currently available (only a few polymorphic states have been predicted by computational models). Structural models and experimental evidence lend support to the view that the Aβ channel is an assembly of loosely associated mobile β-sheet subunits. Here, using planar lipid bilayers and molecular dynamics (MD) simulations, we show that amino acid substitutions can be used to infer which residues are essential for channel structure. We created two Aβ(1-42) peptides with point mutations: F19P and F20C. The substitution of Phe19 with Pro inhibited channel conductance. MD simulation suggests a collapsed pore of F19P channels at the lower bilayer leaflet. The kinks at the Pro residues in the pore-lining β-strands induce blockage of the solvated pore by the N-termini of the chains. The cysteine mutant is capable of forming channels, and the conductance behavior of F20C channels is similar to that of the wild type. Overall, the mutational analysis of the channel activity performed in this work tests the proposition that the channels consist of a β-sheet rich organization, with the charged/polar central strand containing the mutation sites lining the pore, and the C-terminal strands facing the hydrophobic lipid tails. A detailed understanding of channel formation and its structure should aid studies of drug design aiming to control unregulated Aβ-dependent ion fluxes.

Probing Structural Features of Alzheimer’s Amyloid-β Pores in Bilayers Using Site-Specific Amino Acid Substitutions

PubMed Central

2012-01-01

A current hypothesis for the pathology of Alzheimer’s disease (AD) proposes that amyloid-β (Aβ) peptides induce uncontrolled, neurotoxic ion flux across cellular membranes. The mechanism of ion flux is not fully understood because no experiment-based Aβ channel structures at atomic resolution are currently available (only a few polymorphic states have been predicted by computational models). Structural models and experimental evidence lend support to the view that the Aβ channel is an assembly of loosely associated mobile β-sheet subunits. Here, using planar lipid bilayers and molecular dynamics (MD) simulations, we show that amino acid substitutions can be used to infer which residues are essential for channel structure. We created two Aβ1–42 peptides with point mutations: F19P and F20C. The substitution of Phe19 with Pro inhibited channel conductance. MD simulation suggests a collapsed pore of F19P channels at the lower bilayer leaflet. The kinks at the Pro residues in the pore-lining β-strands induce blockage of the solvated pore by the N-termini of the chains. The cysteine mutant is capable of forming channels, and the conductance behavior of F20C channels is similar to that of the wild type. Overall, the mutational analysis of the channel activity performed in this work tests the proposition that the channels consist of a β-sheet rich organization, with the charged/polar central strand containing the mutation sites lining the pore, and the C-terminal strands facing the hydrophobic lipid tails. A detailed understanding of channel formation and its structure should aid studies of drug design aiming to control unregulated Aβ-dependent ion fluxes. PMID:22242635

A comparative study of the effect of Ni9+ and Au8+ ion beams on the properties of poly(methacrylic acid) grafted gum ghatti films

NASA Astrophysics Data System (ADS)

Sharma, Kashma; Kaith, B. S.; Kumar, Vijay; Kumar, Vinod; Kalia, Susheel; Kapur, B. K.; Swart, H. C.

2014-04-01

A systematic comparative study was carried out for the induced changes in the chemical, structural, morphological and thermal properties of poly(methacrylic acid) grafted gum ghatti i.e. [Gg-cl-poly(MAA)] material by irradiation of 120 MeV Ni9+ and Au8+ ions at various fluences ranging from 3×1011 to 3×1012 ions/cm2. The degradation of the material was observed after ion irradiation. A significant loss of crystallinity and change in the crystallite size was observed in irradiated samples of Gg-cl-poly(MAA). The changes in chemical properties and surface morphology were observed by Fourier transform infrared spectroscopy and scanning electron microscopy respectively. The magnitude of the effect of the irradiation was observed to be greater in the case of Au8+ ions irradiation than those of Ni9+ ions irradiation due to the high electronic energy loss of the Au8+ ions in the grafted samples.

Electron source for a mini ion trap mass spectrometer

DOEpatents

Dietrich, D.D.; Keville, R.F.

1995-12-19

An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

Synthesis of sponge-like hydrophobic NiBi3 surface by 200 keV Ar ion implantation

NASA Astrophysics Data System (ADS)

Siva, Vantari; Datta, D. P.; Chatterjee, S.; Varma, S.; Kanjilal, D.; Sahoo, Pratap K.

2017-07-01

Sponge-like nanostructures develop under Ar-ion implantation of a Ni-Bi bilayer with increasing ion fluence at room temperature. The surface morphology features different stages of evolution as a function of ion fluence, finally resulting in a planar surface at the highest fluence. Our investigations on the chemical composition reveal a spontaneous formation of NiBi3 phase on the surface of the as deposited bilayer film. Interestingly, we observe a competition between crystallization and amorphization of the existing poly-crystalline phases as a function of the implanted fluence. Measurements of contact angle by sessile drop method clearly show the ion-fluence dependent hydrophobic nature of the nano-structured surfaces. The wettability has been correlated with the variation in roughness and composition of the implanted surface. In fact, our experimental results confirm dominant effect of ion-sputtering as well as ion-induced mixing at the bilayer interface in the evolution of the sponge-like surface.

Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling.

PubMed

Duncan, Kyle D; Volmer, Dietrich A; Gill, Chris G; Krogh, Erik T

2016-03-01

Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H](-)) ions with limited selective fragmentation. However, carboxylates cationized with Ba(2+) have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba](+) precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH](+) and [BaOH](+)). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

Structural and Biochemical Studies on the Regulation of Biotin Carboxylase by Substrate Inhibition and Dimerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

C Chou; L Tong

2011-12-31

Biotin carboxylase (BC) activity is shared among biotin-dependent carboxylases and catalyzes the Mg-ATP-dependent carboxylation of biotin using bicarbonate as the CO{sub 2} donor. BC has been studied extensively over the years by structural, kinetic, and mutagenesis analyses. Here we report three new crystal structures of Escherichia coli BC at up to 1.9 {angstrom} resolution, complexed with different ligands. Two structures are wild-type BC in complex with two ADP molecules and two Ca{sup 2+} ions or two ADP molecules and one Mg{sup 2+} ion. One ADP molecule is in the position normally taken by the ATP substrate, whereas the other ADPmore » molecule occupies the binding sites of bicarbonate and biotin. One Ca{sup 2+} ion and the Mg{sup 2+} ion are associated with the ADP molecule in the active site, and the other Ca{sup 2+} ion is coordinated by Glu-87, Glu-288, and Asn-290. Our kinetic studies confirm that ATP shows substrate inhibition and that this inhibition is competitive against bicarbonate. The third structure is on the R16E mutant in complex with bicarbonate and Mg-ADP. Arg-16 is located near the dimer interface. The R16E mutant has only a 2-fold loss in catalytic activity compared with the wild-type enzyme. Analytical ultracentrifugation experiments showed that the mutation significantly destabilized the dimer, although the presence of substrates can induce dimer formation. The binding modes of bicarbonate and Mg-ADP are essentially the same as those to the wild-type enzyme. However, the mutation greatly disrupted the dimer interface and caused a large re-organization of the dimer. The structures of these new complexes have implications for the catalysis by BC.« less

Structural and Biochemical Studies on the Regulation of Biotin Carboxylase by Substrate Inhibition and Dimerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chou, Chi-Yuan; Tong, Liang

2012-06-19

Biotin carboxylase (BC) activity is shared among biotin-dependent carboxylases and catalyzes the Mg-ATP-dependent carboxylation of biotin using bicarbonate as the CO{sub 2} donor. BC has been studied extensively over the years by structural, kinetic, and mutagenesis analyses. Here we report three new crystal structures of Escherichia coli BC at up to 1.9 {angstrom} resolution, complexed with different ligands. Two structures are wild-type BC in complex with two ADP molecules and two Ca{sup 2+} ions or two ADP molecules and one Mg{sup 2+} ion. One ADP molecule is in the position normally taken by the ATP substrate, whereas the other ADPmore » molecule occupies the binding sites of bicarbonate and biotin. One Ca{sup 2+} ion and the Mg{sup 2+} ion are associated with the ADP molecule in the active site, and the other Ca{sup 2+} ion is coordinated by Glu-87, Glu-288, and Asn-290. Our kinetic studies confirm that ATP shows substrate inhibition and that this inhibition is competitive against bicarbonate. The third structure is on the R16E mutant in complex with bicarbonate and Mg-ADP. Arg-16 is located near the dimer interface. The R16E mutant has only a 2-fold loss in catalytic activity compared with the wild-type enzyme. Analytical ultracentrifugation experiments showed that the mutation significantly destabilized the dimer, although the presence of substrates can induce dimer formation. The binding modes of bicarbonate and Mg-ADP are essentially the same as those to the wild-type enzyme. However, the mutation greatly disrupted the dimer interface and caused a large re-organization of the dimer. The structures of these new complexes have implications for the catalysis by BC.« less

Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

NASA Astrophysics Data System (ADS)

Zhou, Mowei; Yan, Jing; Romano, Christine A.; Tebo, Bradley M.; Wysocki, Vicki H.; Paša-Tolić, Ljiljana

2018-01-01

Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase, Mnx, from Bacillus sp. PL-12 has been successfully overexpressed in active form as a protein complex with a molecular mass of 211 kDa. We have recently used surface induced dissociation (SID) and ion mobility-mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data from the native mass spectrometry experiments led to a plausible structural model of this multicopper oxidase, which has been difficult to study by conventional structural biology methods. It was also revealed that each Mnx subunit binds a variable number of copper ions. Becasue of the heterogeneity of the protein and limited mass resolution, ambiguities in assigning some of the observed peaks remained as a barrier to fully understanding the role of metals and potential unknown ligands in Mnx. In this study, we performed SID in a modified Fourier transform-ion cyclotron resonance (FTICR) mass spectrometer. The high mass accuracy and resolution offered by FTICR unveiled unexpected artificial modifications on the protein that had been previously thought to be iron bound species based on lower resolution spectra. Additionally, isotopically resolved spectra of the released subcomplexes revealed the metal binding stoichiometry at different structural levels. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes. [Figure not available: see fulltext.

Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 2. Assessing Charge Site Location and Isotope Scrambling

NASA Astrophysics Data System (ADS)

Khakinejad, Mahdiar; Ghassabi Kondalaji, Samaneh; Donohoe, Gregory C.; Valentine, Stephen J.

2016-03-01

Ion mobility spectrometry (IMS) coupled with gas-phase hydrogen deuterium exchange (HDX)-mass spectrometry (MS) and molecular dynamic simulations (MDS) has been used for structural investigation of anions produced by electrospraying a sample containing a synthetic peptide having the sequence KKDDDDDIIKIIK. In these experiments the potential of the analytical method for locating charge sites on ions as well as for utilizing collision-induced dissociation (CID) to reveal the degree of deuterium uptake within specific amino acid residues has been assessed. For diffuse (i.e., more elongated) [M - 2H]2- ions, decreased deuterium content along with MDS data suggest that the D4 and D6 residues are charge sites, whereas for the more diffuse [M - 3H]3- ions, the data suggest that the D4, D7, and the C-terminus are deprotonated. Fragmentation of mobility-selected, diffuse [M - 2H]2- ions to determine deuterium uptake at individual amino acid residues reveals a degree of deuterium retention at incorporation sites. Although the diffuse [M - 3H]3- ions may show more HD scrambling, it is not possible to clearly distinguish HD scrambling from the expected deuterium uptake based on a hydrogen accessibility model. The capability of the IMS-HDX-MS/MS approach to provide relevant details about ion structure is discussed. Additionally, the ability to extend the approach for locating protonation sites on positively-charged ions is presented.

Exploring the coordination change of vanadium and structure transformation of metavanadate MgV2O6 under high pressure

PubMed Central

Tang, Ruilian; Li, Yan; Xie, Shengyi; Li, Nana; Chen, Jiuhua; Gao, Chunxiao; Zhu, Pinwen; Wang, Xin

2016-01-01

Raman spectroscopy, synchrotron angle-dispersive X-ray diffraction (ADXRD), first-principles calculations, and electrical resistivity measurements were carried out under high pressure to investigate the structural stability and electrical transport properties of metavanadate MgV2O6. The results have revealed the coordination change of vanadium ions (from 5+1 to 6) at around 4 GPa. In addition, a pressure-induced structure transformation from the C2/m phase to the C2 phase in MgV2O6 was detected above 20 GPa, and both phases coexisted up to the highest pressure. This structural phase transition was induced by the enhanced distortions of MgO6 octahedra and VO6 octahedra under high pressure. Furthermore, the electrical resistivity decreased with pressure but exhibited different slope for these two phases, indicating that the pressure-induced structural phase transitions of MgV2O6 was also accompanied by the obvious changes in its electrical transport behavior. PMID:27924843

Polymers for Traveling Wave Ion Mobility Spectrometry Calibration

NASA Astrophysics Data System (ADS)

Duez, Quentin; Chirot, Fabien; Liénard, Romain; Josse, Thomas; Choi, ChangMin; Coulembier, Olivier; Dugourd, Philippe; Cornil, Jérôme; Gerbaux, Pascal; De Winter, Julien

2017-07-01

One of the main issues when using traveling wave ion mobility spectrometry (TWIMS) for the determination of collisional cross-section (CCS) concerns the need for a robust calibration procedure built from referent ions of known CCS. Here, we implement synthetic polymer ions as CCS calibrants in positive ion mode. Based on their intrinsic polydispersities, polymers offer in a single sample the opportunity to generate, upon electrospray ionization, numerous ions covering a broad mass range and a large CCS window for different charge states at a time. In addition, the key advantage of polymer ions as CCS calibrants lies in the robustness of their gas-phase structure with respect to the instrumental conditions, making them less prone to collisional-induced unfolding (CIU) than protein ions. In this paper, we present a CCS calibration procedure using sodium cationized polylactide and polyethylene glycol, PLA and PEG, as calibrants with reference CCS determined on a home-made drift tube. Our calibration procedure is further validated by testing the polymer calibration to determine CCS of numerous different ions for which CCS are reported in the literature. [Figure not available: see fulltext.

The interplay of nanointerface curvature and calcium binding in weak polyelectrolyte-coated nanoparticles.

PubMed

Nap, Rikkert J; Gonzalez Solveyra, Estefania; Szleifer, Igal

2018-05-01

When engineering nanomaterials for application in biological systems, it is important to understand how multivalent ions, such as calcium, affect the structural and chemical properties of polymer-modified nanoconstructs. In this work, a recently developed molecular theory was employed to study the effect of surface curvature on the calcium-induced collapse of end-tethered weak polyelectrolytes. In particular, we focused on cylindrical and spherical nanoparticles coated with poly(acrylic acid) in the presence of different amounts of Ca2+ ions. We describe the structural changes that grafted polyelectrolytes undergo as a function of calcium concentration, surface curvature, and morphology. The polymer layers collapse in aqueous solutions that contain sufficient amounts of Ca2+ ions. This collapse, due to the formation of calcium bridges, is not only controlled by the calcium ion concentration but also strongly influenced by the curvature of the tethering surface. The transition from a swollen to a collapsed layer as a function of calcium concentration broadens and shifts to lower amounts of calcium ions as a function of the radius of cylindrical and spherical nanoparticles. The results show how the interplay between calcium binding and surface curvature governs the structural and functional properties of the polymer molecules. This would directly impact the fate of weak polyelectrolyte-coated nanoparticles in biological environments, in which calcium levels are tightly regulated. Understanding such interplay would also contribute to the rational design and optimization of smart interfaces with applications in, e.g., salt-sensitive and ion-responsive materials and devices.

CePt2In7: Shubnikov-de Haas measurements on micro-structured samples under high pressures

NASA Astrophysics Data System (ADS)

Kanter, J.; Moll, P.; Friedemann, S.; Alireza, P.; Sutherland, M.; Goh, S.; Ronning, F.; Bauer, E. D.; Batlogg, B.

2014-03-01

CePt2In7 belongs to the CemMnIn3 m + 2 n heavy fermion family, but compared to the Ce MIn5 members of this group, exhibits a more two dimensional electronic structure. At zero pressure the ground state is antiferromagnetically ordered. Under pressure the antiferromagnetic order is suppressed and a superconducting phase is induced, with a maximum Tc above a quantum critical point around 31 kbar. To investigate the changes in the Fermi Surface and effective electron masses around the quantum critical point, Shubnikov-de Haas measurements were conducted under high pressures in an anvil cell. The samples were micro-structured and contacted using a Focused Ion Beam (FIB). The Focused Ion Beam enables sample contacting and structuring down to a sub-micrometer scale, making the measurement of several samples with complex shapes and multiple contacts on a single anvil feasible.

Mutagenic effect of accelerated heavy ions on bacterial cells

NASA Astrophysics Data System (ADS)

Boreyko, A. V.; Krasavin, E. A.

2011-11-01

The heavy ion accelerators of the Joint Institute for Nuclear Research were used to study the regularities and mechanisms of formation of different types of mutations in prokaryote cells. The induction of direct (lac-, ton B-, col B) mutations for Esherichia coli cells and reverse his- → His+ mutations of Salmonella typhimurium, Bacillus subtilis cells under the action of radiation in a wide range of linear energy transfer (LET) was studied. The regularities of formation of gene and structural (tonB trp-) mutations for Esherichia coli bacteria under the action of accelerated heavy ions were studied. It was demonstrated that the rate of gene mutations as a function of the dose under the action of Γ rays and accelerated heavy ions is described by linear-quadratic functions. For structural mutations, linear "dose-effect" dependences are typical. The quadratic character of mutagenesis dose curves is determined by the "interaction" of two independent "hitting" events in the course of SOS repair of genetic structures. The conclusion made was that gene mutations under the action of accelerated heavy ions are induced by δ electron regions of charged particle tracks. The methods of SOS chromotest, SOS lux test, and λ prophage induction were used to study the regularities of SOS response of cells under the action of radiations in a wide LET range. The following proposition was substantiated: the molecular basis for formation of gene mutations are cluster single-strand DNA breaks, and that for structural mutations, double-strand DNA breaks. It was found out that the LET dependence of the relative biological efficiency of accelerated ions is described by curves with a local maximum. It was demonstrated that the biological efficiency of ionizing radiations with different physical characteristics on cells with different genotype, estimated by the lethal action, induction of gene and deletion mutations, precision excision of transposons, is determined by the specific features of energy transfer of the radiations that affect the character of induced DNA damage, and the efficiency inducible and constitutive cell repair systems. The growth of relative biological efficiency of heavy charged particles is determined by the growth of the damage yield of the DNA participating in the formation of radiation-induced effects, and higher efficiency of inducible repair systems. It was established that the LET value ( L max) for which the maximum (according to the applied irradiation criteria) coefficients of relative biological efficiency are observed varies depending on the character of the registered radiation induced effect. It was demonstrated that for gene mutations and induction of precision excision of mobile elements the values of L max are realized in a LET range of ≈20 keV/μm. For lethal effects of irradiation and induction of deletion mutations the value of L max is ≈ 100 and 50 keV/μm, respectively. The differences in the L max for the studied radiation gene effectis are determined by the different type of DNA damage participating in the mutation process. A molecular model of the formation of gene mutations in Escherichia coli cells under the action of ionizing radiation was proposed. Basic DNA radiation damage and main repair ways were considered in the framework of this model. The basis is the idea of the decisive role of mutagenic, error-prone, branch of SOS repair in fixing premutation DNA damage into point mutations. It was demonstrated that the central mechanism in this process is the formation of an inducible multi-enzymatic complex including the DNA polymerase V (Umu C), RecA-protease, SSB proteins, subunits of DNA polymerase III, performing erroneous DNA synthesis on the damaged matrix. A mathematical model of induction of gene mutations under ultraviolet cell irradiation was developed based on the molecular model.

Structural Transformations in Austenitic Stainless Steel Induced by Deuterium Implantation: Irradiation at 295 K

NASA Astrophysics Data System (ADS)

Morozov, Oleksandr; Zhurba, Volodymir; Neklyudov, Ivan; Mats, Oleksandr; Progolaieva, Viktoria; Boshko, Valerian

2016-02-01

Deuterium thermal desorption spectra were investigated on the samples of austenitic steel 18Cr10NiTi pre-implanted at 295 K with deuterium ions in the dose range from 8 × 1014 to 2.7 × 1018 D/cm2. The kinetics of structural transformation development in the steel layer was traced from deuterium thermodesorption spectra as a function of deuterium concentration. Three characteristic regions with different low rates of deuterium amount desorption as the implantation dose increases were revealed: I—the linear region of low implantation doses (up to 1 × 1017 D/cm2); II—the nonlinear region of medium implantation doses (1 × 1017 to 8 × 1017 D/cm2); III—the linear region of high implantation doses (8 × 1017 to 2.7 × 1018 D/cm2). During the process of deuterium ion irradiation, the coefficient of deuterium retention in steel varies in discrete steps. Each of the discrete regions of deuterium retention coefficient variation corresponds to different implanted-matter states formed during deuterium ion implantation. The low-dose region is characterized by formation of deuterium-vacancy complexes and solid-solution phase state of deuterium in the steel. The total concentration of the accumulated deuterium in this region varies between 2.5 and 3 at.%. The medium-dose region is characterized by the radiation-induced action on the steel in the presence of deuterium with the resulting formation of the energy-stable nanosized crystalline structure of steel, having a developed network of intercrystalline boundaries. The basis for this developed network of intercrystalline boundaries is provided by the amorphous state, which manifests itself in the thermodesorption spectra as a widely temperature-scale extended region of deuterium desorption (structure formation with a varying activation energy). The total concentration of the accumulated deuterium in the region of medium implantation doses makes 7 to 8 at.%. The resulting structure shows stability against the action of deuterium ion implantation. This manifests itself in a nearly complete ceasing of deuterium accumulation from a newly implanted dose (radiation-resistant structure).

3D-structured illumination microscopy reveals clustered DNA double-strand break formation in widespread γH2AX foci after high LET heavy-ion particle radiation

PubMed Central

Hagiwara, Yoshihiko; Niimi, Atsuko; Isono, Mayu; Yamauchi, Motohiro; Yasuhara, Takaaki; Limsirichaikul, Siripan; Oike, Takahiro; Sato, Hiro; Held, Kathryn D.; Nakano, Takashi; Shibata, Atsushi

2017-01-01

DNA double-strand breaks (DSBs) induced by ionising radiation are considered the major cause of genotoxic mutations and cell death. While DSBs are dispersed throughout chromatin after X-rays or γ-irradiation, multiple types of DNA damage including DSBs, single-strand breaks and base damage can be generated within 1–2 helical DNA turns, defined as a complex DNA lesion, after high Linear Energy Transfer (LET) particle irradiation. In addition to the formation of complex DNA lesions, recent evidence suggests that multiple DSBs can be closely generated along the tracks of high LET particle irradiation. Herein, by using three dimensional (3D)-structured illumination microscopy, we identified the formation of 3D widespread γH2AX foci after high LET carbon-ion irradiation. The large γH2AX foci in G2-phase cells encompassed multiple foci of replication protein A (RPA), a marker of DSBs undergoing resection during homologous recombination. Furthermore, we demonstrated by 3D analysis that the distance between two individual RPA foci within γH2AX foci was approximately 700 nm. Together, our findings suggest that high LET heavy-ion particles induce clustered DSB formation on a scale of approximately 1 μm3. These closely localised DSBs are considered to be a risk for the formation of chromosomal rearrangement after heavy-ion irradiation. PMID:29312614

Heavy-ion induced electronic desorption of gas from metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molvik, A W; Kollmus, H; Mahner, E

During heavy ion operation in several particle accelerators world-wide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion induced gas desorption scales with the electronic energy loss (dE{sub e}/d/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

Feasibility of atomic and molecular laser-induced breakdown spectroscopy (LIBS) to in situ determination of chlorine in concrete : summary.

DOT National Transportation Integrated Search

2016-10-01

One of the most serious threats to Floridas extensive coastal transportation infrastructure is the invasion of steel-reinforced concrete structures by chloride ions. In this project, University of Florida researchers investigated the use of a nove...

Modification of structural and magnetic properties of soft magnetic multi-component metallic glass by 80 MeV 16O6+ ion irradiation

NASA Astrophysics Data System (ADS)

Kane, S. N.; Shah, M.; Satalkar, M.; Gehlot, K.; Kulriya, P. K.; Avasthi, D. K.; Sinha, A. K.; Modak, S. S.; Ghodke, N. L.; Reddy, V. R.; Varga, L. K.

2016-07-01

Effect of 80 MeV 16O6+ ion irradiation in amorphous Fe77P8Si3C5Al2Ga1B4 alloy is reported. Electronic energy loss induced modifications in the structural and, magnetic properties were monitored by synchrotron X-ray diffraction (SXRD), Mössbauer and, magnetic measurements. Broad amorphous hump seen in SXRD patterns reveals the amorphous nature of the studied specimens. Mössbauer measurements suggest that: (a) alignment of atomic spins within ribbon plane, (b) changes in average hyperfine field suggests radiation-induced decrease in the inter atomic distance around Mössbauer (Fe) atom, (c) hyperfine field distribution confirms the presence of non-magnetic elements (e.g. - B, P, C) in the first near-neighbor shell of the Fe atom, thus reducing its magnetic moment, and (d) changes in isomer shift suggests variation in average number of the metalloid near neighbors and their distances. Minor changes in soft magnetic behavior - watt loss and, coercivity after an irradiation dose of 2 × 1013 ions/cm2 suggests prospective application of Fe77P8Si3C5Al2Ga1B4 alloy as core material in accelerators (radio frequency cavities).

Study of thickness dependent sputtering in gold thin films by swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Dash, P.; Sahoo, P. K.; Solanki, V.; Singh, U. B.; Avasthi, D. K.; Mishra, N. C.

2015-12-01

Gold thin films of varying thickness (10-100 nm) grown on silica substrates by e-beam evaporation method were irradiated by 120 MeV Au ions at 3 × 1012 and 1 × 1013 ions cm-2 fluences. Irradiation induced modifications of these films were probed by glancing angle X-ray diffraction (GAXRD), atomic force microscopy (AFM), Rutherford backscattering spectrometry (RBS) and surface enhanced Raman scattering (SERS). Irradiation didn't affect the structure, the lattice parameter or the crystallite size, but modified the texturing of grains from [1 1 1] to [2 2 0]. RBS indicated thickness dependent sputtering on irradiation. The sputtering yield was found to decrease with increasing thickness. AFM indicated increase of roughness with increasing irradiation fluence for films of all thickness. In agreement with the AFM observation, the gold nanostructures on the surface of 20 nm thick film were found to increase the SERS signal of acridine orange dye attached to these structures. The SERS peaks were amplified by many fold with increasing ion fluence. The effect of 120 MeV Au ion irradiation on the grain texture, surface morphology and SERS activity in addition to the thickness dependent sputtering in gold thin films are explained by the thermal spike model of ion-matter interaction.

Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.

PubMed

Lucks, Christian; Rossberg, André; Tsushima, Satoru; Foerstendorf, Harald; Fahmy, Karim; Bernhard, Gert

2013-10-07

Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond.

Conformational studies of the capsular polysaccharide produced by Neisseria meningitidis group A.

PubMed

Foschiatti, Michela; Hearshaw, Meredith; Cescutti, Paola; Ravenscroft, Neil; Rizzo, R

2009-05-12

The effect of different cations on the conformational and morphological properties of the capsular polysaccharide produced by Neisseria meningitidis group A was investigated. Circular dichroism studies showed that the presence of Na(+), NH4+ or Ca(2+) ions induced different local conformations of the polysaccharide chain through interactions with the phosphodiester group bridging the saccharide residues in the polymer chain. Atomic force microscopy experiments confirmed that the morphology of the polysaccharide chains was different depending on the nature of the counterion. Ammonium ions were associated with the presence of single polymer chains in an elongated conformation, whereas sodium ions favored the folding of the chains into a globular conformation. The addition of calcium ions produced the aggregation of a limited number of globular polysaccharide chains to form a 'toroidal-like' structure.

Phase transformations in ion-irradiated silicides

NASA Technical Reports Server (NTRS)

Hewett, C. A.; Lau, S. S.; Suni, I.; Hung, L. S.

1985-01-01

The present investigation has three objectives. The first is concerned with the phase transformation of CoSi2 under ion implantation and the subsequent crystallization characteristics during annealing, taking into account epitaxial and nonepitaxial recrystallization behavior. The second objective is related to a study of the general trend of implantation-induced damage and crystallization behavior for a number of commonly used silicides. The last objective involves a comparison of the recrystallization behavior of cosputtered refractory silicides with that of the ion-implanted silicides. It was found that epitaxial regrowth of ion-irradiated CoSi2 occurred for samples with an epitaxial seed left at the Si/CoSi2 interface. A structural investigation of CoSi2 involving transmission electron microscopy (TEM) showed that after high-dose implantation CoSi2 is amorphous.

Low-loss and tunable near-zero-epsilon titanium nitride

NASA Astrophysics Data System (ADS)

Popović, M.; Novaković, M.; Schmidt, E.; Schöppe, P.; Bibić, N.; Ronning, C.; Rakočević, Z.

2017-10-01

Titanium nitride (TiN) has emerged as alternative plasmonic material in the visible and near-infrared spectral range due to its metallic properties. We studied the influence of silver ion implantation (fluence range from 0.5 × 1016-6 × 1016 ions/cm2) on the structural and optical properties of reactively sputtered 260 nm thick TiN films. The columnar structure was partially destroyed by the irradiation and up to 5 at.% of Ag was incorporated into the films within the projected ion range. The formation of cubic Ag nanoparticles with size of 1-2 nm was observed by high resolution transmission electron microscopy and subsequent fast Fourier transform analysis. This presence of Ag within the TiN matrix drastically changes both the real and imaginary component of the dielectric function and provides low optical losses. A Drude Lorentz dielectric analysis based on free electron and oscillator model are carried out to describe the silver influence on the optical behavior of TiN. With increasing ion fluence, the unscreened plasma frequency decreased and broadening increased. The energy, strength and broadening of the interband transitions were studied with respect to the silver ion fluence and correlated with the microstructural changes induced in TiN films.

A salient effect of density on the dynamics of nonaqueous electrolytes.

PubMed

Han, Sungho

2017-04-24

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Valence, exchange interaction, and location of Mn ions in polycrystalline M n x G a 1 - x N ( x ≤ 0.04 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Furrer, A.; Kramer, K. W.; Podlesnyak, A.

In this paper, we present an experimental study for polycrystalline samples of the diluted magnetic semiconductormore » $$\\mathrm{M}{\\mathrm{n}}_{x}\\mathrm{G}{\\mathrm{a}}_{1{-}x}\\mathrm{N}(x{\\le}0.04)$$ in order to address some of the existing controversial issues. X-ray and neutron diffraction, x-ray absorption near-edge structure, and electron paramagnetic resonance experiments were used to characterize the structural, electronic, and magnetic properties of the samples, and inelastic neutron scattering was employed to determine the magnetic excitations associated with Mn monomers and dimers. Our main conclusions are as follows: (i) The valence of the Mn ions is $2+$. (ii) The $$\\mathrm{M}{\\mathrm{n}}^{2+}$$ ions experience a substantial single-ion axial anisotropy with parameter D = 0.027(3) meV. (iii) Nearest-neighbor $$\\mathrm{M}{\\mathrm{n}}^{2+}$$ ions are coupled antiferromagnetically. Finally, the exchange parameter $$J={-}0.140(7)\\mathrm{meV}$$ is independent of the Mn content $x$; i.e., there is no evidence for hole-induced modifications of $J$ towards a potentially high Curie temperature postulated in the literature.« less

A salient effect of density on the dynamics of nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Han, Sungho

2017-04-01

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Valence, exchange interaction, and location of Mn ions in polycrystalline M n x G a 1 - x N ( x ≤ 0.04 )

DOE PAGES

Furrer, A.; Kramer, K. W.; Podlesnyak, A.; ...

2018-04-10

In this paper, we present an experimental study for polycrystalline samples of the diluted magnetic semiconductormore » $$\\mathrm{M}{\\mathrm{n}}_{x}\\mathrm{G}{\\mathrm{a}}_{1{-}x}\\mathrm{N}(x{\\le}0.04)$$ in order to address some of the existing controversial issues. X-ray and neutron diffraction, x-ray absorption near-edge structure, and electron paramagnetic resonance experiments were used to characterize the structural, electronic, and magnetic properties of the samples, and inelastic neutron scattering was employed to determine the magnetic excitations associated with Mn monomers and dimers. Our main conclusions are as follows: (i) The valence of the Mn ions is $2+$. (ii) The $$\\mathrm{M}{\\mathrm{n}}^{2+}$$ ions experience a substantial single-ion axial anisotropy with parameter D = 0.027(3) meV. (iii) Nearest-neighbor $$\\mathrm{M}{\\mathrm{n}}^{2+}$$ ions are coupled antiferromagnetically. Finally, the exchange parameter $$J={-}0.140(7)\\mathrm{meV}$$ is independent of the Mn content $x$; i.e., there is no evidence for hole-induced modifications of $J$ towards a potentially high Curie temperature postulated in the literature.« less

On the function and fate of chloride ions in amyloidogenic self-assembly of insulin in an acidic environment: salt-induced condensation of fibrils.

PubMed

Babenko, Viktoria; Surmacz-Chwedoruk, Weronika; Dzwolak, Wojciech

2015-02-24

Formation of amyloid fibrils is often facilitated in the presence of specific charge-compensating ions. Dissolved sodium chloride is known to accelerate insulin fibrillation at low pH that has been attributed to the shielding of electrostatic repulsion between positively charged insulin molecules by chloride ions. However, the subsequent fate of Cl(-) anions; that is, possible entrapment within elongating fibrils or escape into the bulk solvent, remains unclear. Here, we show that, while the presence of NaCl at the onset of insulin aggregation induces structural variants of amyloid with distinct fingerprint infrared features, a delayed addition of salt to fibrils that have been already formed in its absence and under quiescent conditions triggers a "condensation effect": amyloid superstructures with strong chiroptical properties are formed. Chloride ions appear to stabilize these superstructures in a manner similar to stabilization of DNA condensates by polyvalent cations. The concentration of residual chloride ions trapped within bovine insulin fibrils grown in 0.1 M NaCl, at pD 1.9, and rinsed extensively with water afterward is less than 1 anion per 16 insulin monomers (as estimated using ion chromatography) implying absence of defined solvent-sequestered nesting sites for chloride counterions. Our results have been discussed in the context of mechanisms of insulin aggregation.

Ion beam modification of structural and optical properties of GeO2 thin films deposited at various substrate temperatures using pulsed laser deposition

NASA Astrophysics Data System (ADS)

Rathore, Mahendra Singh; Vinod, Arun; Angalakurthi, Rambabu; Pathak, A. P.; Singh, Fouran; Thatikonda, Santhosh Kumar; Nelamarri, Srinivasa Rao

2017-11-01

High energy heavy ion irradiation-induced modification of high quality crystalline GeO2 thin films grown at different substrate temperatures ranging from 100 to 500 °C using pulsed laser deposition has been investigated. The pristine films were irradiated with 100 MeV Ag7+ ions at fixed fluence of 1 × 1013 ions/cm2. These pristine and irradiated films have been characterized using X-ray diffraction, atomic force microscopy, Raman spectroscopy, Fourier transform infrared and photoluminescence spectroscopy. The XRD and Raman results of pristine films confirm the formation of hexagonal structure of GeO2 films, whereas the irradiation eliminates all the peaks except major GeO2 peak of (101) plane. It is evident from the XRD results that crystallite size changes with substrate temperature and SHI irradiation. The surface morphology of films was studied by AFM. The functional group of pristine and irradiated films was investigated by IR transmission spectra. Pristine films exhibited strong photoluminescence around 342 and 470 nm due to oxygen defects and a red shift in the PL bands is observed after irradiation. Possible mechanism of tuning structural and optical properties of pristine as well as irradiated GeO2 films with substrate temperature and ion beam irradiation has been reported in detail.

Gas chromatography/chemical ionization triple quadrupole mass spectrometry analysis of anabolic steroids: ionization and collision-induced dissociation behavior.

PubMed

Polet, Michael; Van Gansbeke, Wim; Van Eenoo, Peter; Deventer, Koen

2016-02-28

The detection of new anabolic steroid metabolites and new designer steroids is a challenging task in doping analysis. Switching from electron ionization gas chromatography triple quadrupole mass spectrometry (GC/EI-MS/MS) to chemical ionization (CI) has proven to be an efficient way to increase the sensitivity of GC/MS/MS analyses and facilitate the detection of anabolic steroids. CI also extends the possibilities of GC/MS/MS analyses as the molecular ion is retained in its protonated form due to the softer ionization. In EI it can be difficult to find previously unknown but expected metabolites due to the low abundance or absence of the molecular ion and the extensive (and to a large extent unpredictable) fragmentation. The main aim of this work was to study the CI and collision-induced dissociation (CID) behavior of a large number of anabolic androgenic steroids (AAS) as their trimethylsilyl derivatives in order to determine correlations between structures and CID fragmentation. Clarification of these correlations is needed for the elucidation of structures of unknown steroids and new metabolites. The ionization and CID behavior of 65 AAS have been studied using GC/CI-MS/MS with ammonia as the reagent gas. Glucuronidated AAS reference standards were first hydrolyzed to obtain their free forms. Afterwards, all the standards were derivatized to their trimethylsilyl forms. Full scan and product ion scan analyses were used to examine the ionization and CID behavior. Full scan and product ion scan analyses revealed clear correlations between AAS structure and the obtained mass spectra. These correlations were confirmed by analysis of multiple hydroxylated, methylated, chlorinated and deuterated analogs. AAS have been divided into three groups according to their ionization behavior and into seven groups according to their CID behavior. Correlations between fragmentation and structure were revealed and fragmentation pathways were postulated. Copyright © 2016 John Wiley & Sons, Ltd.

Ca2+-induced phase separation in black lipid membranes and its effect on the transport of a hydrophobic ion.

PubMed

Miller, A; Schmidt, G; Eibl, H; Knoll, W

1985-03-14

Voltage jump-current relaxation studies have been performed with dipicrylamine-doped black membranes of binary lipid mixtures. As in the case of the carrier-mediated ion transport (Schmidt, G., Eibl, H. and Knoll, W. (1982) J. Membrane Biol. 70, 147-155) no evidence was found that the neutral lipid phosphatidylcholine (DPMPC) and the charged phosphatidic acid (DPMPA) are heterogeneously distributed in the membrane over the whole range of composition. However, besides a continuous dilution of the surface charges of DPMPA by the addition of DPMPC molecules, different structural properties of mixed membranes influence the kinetics of the dipicrylamine transport. The addition of Ca2+ to the electrolyte induces a lipid phase separation within the membrane into two fluid phases of distinctly different characteristics of the translocation of hydrophobic ions. Thus, it is possible to determine a preliminary composition phase diagram for the DPMPA/DPMPC mixtures as a function of the Ca2+ concentration.

Ferroelectric properties of Pb(Zr,Ti)O3 films under ion-beam induced strain

NASA Astrophysics Data System (ADS)

Lee, Jung-Kun; Nastasi, Michael

2012-11-01

The influence of an ion-beam induced biaxial stress on the ferroelectric and dielectric properties of Pb(Zr,Ti)O3 (PZT) films is investigated using the ion beam process as a novel approach to control external stress. Tensile stress is observed to decrease the polarization, permittivity, and ferroelectric fatigue resistance of the PZT films whose structure is monoclinic. However, a compressive stress increases all of them in monoclinic PZT films. The dependence of the permittivity on stress is found not to follow the phenomenological theory relating external forces to intrinsic properties of ferroelectric materials. Changes in the ferroelectric and dielectric properties indicate that the application of a biaxial stress modulates both extrinsic and intrinsic properties of PZT films. Different degrees of dielectric non-linearity suggests the density and mobility of non-180o domain walls, and the domain switching can be controlled by an applied biaxial stress and thereby influence the ferroelectric and dielectric properties.

Copper-zinc superoxide dismutase is activated through a sulfenic acid intermediate at a copper ion entry site.

PubMed

Fetherolf, Morgan M; Boyd, Stefanie D; Taylor, Alexander B; Kim, Hee Jong; Wohlschlegel, James A; Blackburn, Ninian J; Hart, P John; Winge, Dennis R; Winkler, Duane D

2017-07-21

Metallochaperones are a diverse family of trafficking molecules that provide metal ions to protein targets for use as cofactors. The copper chaperone for superoxide dismutase (Ccs1) activates immature copper-zinc superoxide dismutase (Sod1) by delivering copper and facilitating the oxidation of the Sod1 intramolecular disulfide bond. Here, we present structural, spectroscopic, and cell-based data supporting a novel copper-induced mechanism for Sod1 activation. Ccs1 binding exposes an electropositive cavity and proposed "entry site" for copper ion delivery on immature Sod1. Copper-mediated sulfenylation leads to a sulfenic acid intermediate that eventually resolves to form the Sod1 disulfide bond with concomitant release of copper into the Sod1 active site. Sod1 is the predominant disulfide bond-requiring enzyme in the cytoplasm, and this copper-induced mechanism of disulfide bond formation obviates the need for a thiol/disulfide oxidoreductase in that compartment. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yadav, Praveen Kumar, E-mail: praveenyadav@rrcat.gov.in; Nayak, Maheswar; Rai, Sanjay Kumar

The authors report the effect of argon ion to molybdenum atom ratio (r) on the microstructure of low energy (70 eV) argon ion assisted electron beam evaporated Mo thin films. Surface roughness, morphology, and crystallinity of Mo films are found to strongly depend on “r.” Increase of “r” from 0 to 100 induces gradual loss in crystallinity, reduction in surface roughness and systematic increase in density of the film. For “r” ∼ 100, average atomic density of the film approaches the bulk value (97%) with lowest surface roughness. Further, increasing “r” up to 170 reduces the atomic density, increases roughness, and increase inmore » crystallinity induced by low energy Ar ion beam. The observed surface roughness and grain size determined by x-ray reflectivity and glancing incidence x-ray diffraction correlate well with atomic force microscopy measurements. This study demonstrates that for r = 100 one gets lowest roughness Mo film with highest density and nearly amorphous microstructure. The growth model is discussed by structural zone model.« less

Atomic mixing induced by swift heavy ion irradiation of Fe/Zr multilayers

NASA Astrophysics Data System (ADS)

Jaouen, C.; Michel, A.; Pacaud, J.; Dufour, C.; Bauer, Ph.; Gervais, B.

1999-01-01

The mechanism of ion induced mixing and phase change was studied for Fe/Zr multilayers, and specifically for the case of swift heavy ions giving rise to a very large electronic excitation of the target. The multilayers had a modulation of 7.6 nm and an overall composition Fe 69Zr 31. The Zr layers were amorphous whereas the Fe ones were crystalline (bcc) with a very strong (1 1 0) texture in the growth direction. The phase transformation and the composition changes were analysed using the structural and magnetic properties of the Fe component by means of a detailed analysis of the X-ray diffraction profiles and with the aid of backscattering Mössbauer spectroscopy. A complete mixing was observed at a fluence of 10 13 U/cm 2. Both phenomena, the dose dependence of the ion beam mixed amorphous non-magnetic phase and the quantitative evolution of the crystalline iron layer thickness, suggest that mixing occurs in a two-stage process. At an initial stage, an anisotropic diffusion of iron atoms in the amorphous zirconium layers takes place along the interface, while subsequent ion bombardment leads to a generalised transformation through the whole of the Fe layer. Finally, the implications of these observations are discussed in comparison to the plastic deformation phenomena reported for amorphous alloys.

Formation, stability and dissociation dynamics of {{\\rm{N}}}_{2}{}^{{\\rm{n}}+} cations (n = 1 - 2) in 3.5 keV e - -N2 collisions studied using the energy resolved electron-ion coincidence technique

NASA Astrophysics Data System (ADS)

Kumar, S.; Prajapati, S.; Singh, B.; Singh, B. K.; Shanker, R.

2018-04-01

Coincidences between energy selected electrons and ions produced in the decay of a core hole ionized (excited) state in a free nitrogen molecule have been measured at three specified energies of emitted electrons to reveal the individual pathways produced in 3.5 keV electron-induced fragmentation processes. From these measurements, it has been possible to show, for the first time, that in addition to the normal Auger decay, the resonant Auger excitation channels also share their appreciable contributions in producing singly charged parent ions in an electron-induced collision system. The correlations between ion fragmentation products and electronic structures with a hole configuration in singly-, doubly- and possibly in triply charged molecular electronic states populated in the electronic decay of the initial core hole have been studied and discussed. KER values obtained from our experiments are found to be consistent with the previous results of photo absorption experiments for fragmentation channel {{{{N}}}2}2+ → N+ + N+ however, N2+ fragment ions are found to arise mainly from the fragmentation channel {{{{N}}}2}2+ → N2+ + N and to possess relatively low kinetic energies in the considered region of binding energies.

Pressure induced structural phase transition from NaCl-type (B1) to CsCl-type (B2) structure in sodium chloride

NASA Astrophysics Data System (ADS)

Jain, Aayushi; Dixit, R. C.

2018-05-01

Pressure induced structural phase transition of NaCl-type (B1) to CsCl-type (B2) structure in Sodium Chloride NaCl are presented. An effective interionic interaction potential (EIOP) with long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge is reported here. The reckon value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are compatible as compared with reported data. The variations of elastic constants and their combinations with pressure follow ordered behavior. The present approach has also succeeded in predicting the Born and relative stability criteria.

Dynamic defect annealing in wurtzite MgZnO implanted with Ar ions

NASA Astrophysics Data System (ADS)

Azarov, A. Yu.; Wendler, E.; Du, X. L.; Kuznetsov, A. Yu.; Svensson, B. G.

2015-09-01

Successful implementation of ion beams for modification of ternary ZnO-based oxides requires understanding and control of radiation-induced defects. Here, we study structural disorder in wurtzite ZnO and MgxZn1-xO (x ⩽ 0.3) samples implanted at room and 15 K temperatures with Ar ions in a wide fluence range (5 × 1012-3 × 1016 cm-2). The samples were characterized by Rutherford backscattering/channeling spectrometry performed in-situ without changing the sample temperature. The results show that all the samples exhibit high radiation resistance and cannot be rendered amorphous even for high ion fluences. Increasing the Mg content leads to some damage enhancement near the surface region; however, irrespective of the Mg content, the fluence dependence of bulk damage in the samples displays the so-called IV-stage evolution with a reverse temperature effect for high ion fluences.

Numerical experiments on charging of a spherical body in a plasma with Maxwellian distributions of charged particles

NASA Astrophysics Data System (ADS)

Krasovsky, Victor L.; Kiselyov, Alexander A.

2017-12-01

New results of numerical simulation of collisionless plasma perturbation caused by a sphere absorbing electrons and ions are presented. Consideration is given to nonstationary phenomena accompanying the process of charging as well as to plasma steady state reached at long times. Corresponding asymptotic values of charges of the sphere and trapped-ion cloud around it have been found along with self-consistent electric field pattern depending on parameters of the unperturbed plasma. It is established that contribution of the trapped ions to screening of the charged sphere can be quite significant, so that the screening becomes essentially nonlinear in nature. A simple interconnection between the sphere radius, electron and ion Debye lengths has been revealed as the condition for maximum trapped-ion effect. Kinetic structure of the space charge induced in the plasma is discussed with relation to the specific form of the unperturbed charged particle distribution functions.

Heavy doping of CdTe single crystals by Cr ion implantation

NASA Astrophysics Data System (ADS)

Popovych, Volodymyr D.; Böttger, Roman; Heller, Rene; Zhou, Shengqiang; Bester, Mariusz; Cieniek, Bogumil; Mroczka, Robert; Lopucki, Rafal; Sagan, Piotr; Kuzma, Marian

2018-03-01

Implantation of bulk CdTe single crystals with high fluences of 500 keV Cr+ ions was performed to achieve Cr concentration above the equilibrium solubility limit of this element in CdTe lattice. The structure and composition of the implanted samples were studied using secondary ion mass spectrometry (SIMS), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS) to characterize the incorporation of chromium into the host lattice and to investigate irradiation-induced damage build-up. It was found that out-diffusion of Cr atoms and sputtering of the targets alter the depth distribution and limit concentration of the projectile ions in the as-implanted samples. Appearance of crystallographically oriented, metallic α-Cr nanoparticles inside CdTe matrix was found after implantation, as well as a strong disorder at the depth far beyond the projected range of the implanted ions.

Strain tunable magnetic properties of 3d transition-metal ion doped monolayer MoS2: A first-principles study

NASA Astrophysics Data System (ADS)

Zhu, Yupeng; Liang, Xiao; Qin, Jun; Deng, Longjiang; Bi, Lei

2018-05-01

In this article, a systematic study on the magnetic properties and strain tunability of 3d transition metal ions (Mn, Fe, Co, Ni) doped MoS2 using first-principles calculations is performed. Antiferromagnetic coupling is observed between Mn, Fe ions and the nearest neighbor Mo ions; whereas ferromagnetic coupling is observed in Co and Ni systems. It is also shown that by applying biaxial tensile strain, a significant change of the magnetic moment is observed in all transition metal doped MoS2 materials with a strain threshold. The changes of total magnetic moment have different mechanisms for different doping systems including an abrupt change of the bond lengths, charge transfer and strain induced structural anisotropy. These results demonstrate applying strain as a promising method for tuning the magnetic properties in transition metal ion doped monolayer MoS2.

Effect of protonation and deprotonation on the gas-phase reactivity of fluorinated 1,2,4-triazines.

PubMed

Giorgi, Gianluca; Palumbo Piccionello, Antonio; Pace, Andrea; Buscemi, Silvestre

2008-05-01

Positive and negative electrospray mass spectrometry (MS), in-time and in-space MS(n) experiments, high-resolution and accurate mass measurements obtained with an Orbitrap, together with density functional theory calculations have been used to study the gas-phase ion chemistry of a series of fluorinated 1,2,4-triazines. As a result of low-energy collision-induced dissociations, occurring in an ion trap and in a triple quadrupole, their protonated and deprotonated molecules show interesting features depending on the nature and structure of the precursor ions. The occurrence of elimination/hydration reactions produced by positive ions in the ion trap is noteworthy. Decompositions of deprotonated molecules, initiated by elimination of a hydroxyl radical from [M-H](-), are dominated by radical anions. Theoretical calculations have allowed us to obtain information on atom sites involved in the protonation and deprotonation reactions.

Main-ion intrinsic toroidal rotation profile driven by residual stress torque from ion temperature gradient turbulence in the DIII-D tokamak

DOE PAGES

Grierson, B. A.; Wang, W. X.; Ethier, S.; ...

2017-01-06

Intrinsic toroidal rotation of the deuterium main ions in the core of the DIII-D tokamak is observed to transition from flat to hollow, forming an off-axis peak, above a threshold level of direct electron heating. Nonlinear gyrokinetic simulations show that the residual stress associated with electrostatic ion temperature gradient turbulence possesses the correct radial location and stress structure to cause the observed hollow rotation profile. Residual stress momentum flux in the gyrokinetic simulations is balanced by turbulent momentum diffusion, with negligible contributions from turbulent pinch. Finally, the prediction of the velocity profile by integrating the momentum balance equation produces amore » rotation profile that qualitatively and quantitatively agrees with the measured main-ion profile, demonstrating that fluctuation-induced residual stress can drive the observed intrinsic velocity profile.« less

Influence of the normalized ion flux on the constitution of alumina films deposited by plasma-assisted chemical vapor deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurapov, Denis; Reiss, Jennifer; Trinh, David H.

2007-07-15

Alumina thin films were deposited onto tempered hot working steel substrates from an AlCl{sub 3}-O{sub 2}-Ar-H{sub 2} gas mixture by plasma-assisted chemical vapor deposition. The normalized ion flux was varied during deposition through changes in precursor content while keeping the cathode voltage and the total pressure constant. As the precursor content in the total gas mixture was increased from 0.8% to 5.8%, the deposition rate increased 12-fold, while the normalized ion flux decreased by approximately 90%. The constitution, morphology, impurity incorporation, and the elastic properties of the alumina thin films were found to depend on the normalized ion flux. Thesemore » changes in structure, composition, and properties induced by normalized ion flux may be understood by considering mechanisms related to surface and bulk diffusion.« less

Influence of 400 keV carbon ion implantation on structural, optical and electrical properties of PMMA

NASA Astrophysics Data System (ADS)

Arif, Shafaq; Rafique, M. Shahid; Saleemi, Farhat; Sagheer, Riffat; Naab, Fabian; Toader, Ovidiu; Mahmood, Arshad; Rashid, Rashad; Mahmood, Mazhar

2015-09-01

Ion implantation is a useful technique to modify surface properties of polymers without altering their bulk properties. The objective of this work is to explore the 400 keV C+ ion implantation effects on PMMA at different fluences ranging from 5 × 1013 to 5 × 1015 ions/cm2. The surface topographical examination of irradiated samples has been performed using Atomic Force Microscope (AFM). The structural and chemical modifications in implanted PMMA are examined by Raman and Fourier Infrared Spectroscopy (FTIR) respectively. The effects of carbon ion implantation on optical properties of PMMA are investigated by UV-Visible spectroscopy. The modifications in electrical conductivity have been measured using a four point probe technique. AFM images reveal a decrease in surface roughness of PMMA with an increase in ion fluence from 5 × 1014 to 5 × 1015 ions/cm2. The existence of amorphization and sp2-carbon clusterization has been confirmed by Raman and FTIR spectroscopic analysis. The UV-Visible data shows a prominent red shift in absorption edge as a function of ion fluence. This shift displays a continuous reduction in optical band gap (from 3.13 to 0.66 eV) due to formation of carbon clusters. Moreover, size of carbon clusters and photoconductivity are found to increase with increasing ion fluence. The ion-induced carbonaceous clusters are believed to be responsible for an increase in electrical conductivity of PMMA from (2.14 ± 0.06) × 10-10 (Ω-cm)-1 (pristine) to (0.32 ± 0.01) × 10-5 (Ω-cm)-1 (irradiated sample).

N+ ion-target interactions in PPO polymer: A structural characterization

NASA Astrophysics Data System (ADS)

Das, A.; Dhara, S.; Patnaik, A.

1999-01-01

N + ion beam induced effects on the spin coated amorphous poly(2,6-dimethyl phenylene oxide) (PPO) films in terms of chemical structure and electronic and vibrational properties were investigated using Fourier Transform Infrared spectroscopy (FTIR) and Ultraviolet-Visible (UV-VIS) spectroscopy. Both techniques revealed that the stability of PPO was very weak towards 100 keV N + ions revealing the threshold fluence to be 10 14 ions/cm 2 for fragmentation of the polymer. FTIR analysis showed disappearance of all characteristic IR bands at a total fluence of 10 14 ions/cm 2 except for the band CC at 1608 cm -1 which was found to shift to a lower wave number along with an enhancement in the full width half maximum (FWHM) value with increasing fluence. A new bond appeared due to oxidation as a shoulder at 1680 cm -1 in FTIR spectra indicating the presence of CO type bond as a result of N + implantation on PPO films. The optical band gap ( Eg) deduced from absorption spectra, was observed to decrease from 4.4 to 0.5 eV with fluence. The implantation induced carbonaceous clusters, determined using Robertson's formula for the optical band gap, were found to consist of ˜160 fused hexagonal aromatic rings at the maximum energy fluence. An enhanced absorption coefficient as a function of fluence indicated incorporation of either much larger concentration of charge carriers or their mobility than that of the pristine sample. Calculated band tail width from Urbach band tail region for the implanted samples pointed the band edge sharpness to be strongly dependent on fluence indicating an increased disorder with increasing fluence.

Predicting Electrostatic Forces in RNA Folding

PubMed Central

Tan, Zhi-Jie; Chen, Shi-Jie

2016-01-01

Metal ion-mediated electrostatic interactions are critical to RNA folding. Although considerable progress has been made in mechanistic studies, the problem of accurate predictions for the ion effects in RNA folding remains unsolved, mainly due to the complexity of several potentially important issues such as ion correlation and dehydration effects. In this chapter, after giving a brief overview of the experimental findings and theoretical approaches, we focus on a recently developed new model, the tightly bound ion (TBI) model, for ion electrostatics in RNA folding. The model is unique because it can treat ion correlation and fluctuation effects for realistic RNA 3D structures. For monovalent ion (such as Na+) solutions, where ion correlation is weak, TBI and the Poisson–Boltzmann (PB) theory give the same results and the results agree with the experimental data. For multivalent ion (such as Mg2+) solutions, where ion correlation can be strong, however, TBI gives much improved predictions than the PB. Moreover, the model suggests an ion correlation- induced mechanism for the unusual efficiency of Mg2+ ions in the stabilization of RNA tertiary folds. In this chapter, after introducing the theoretical framework of the TBI model, we will describe how to apply the model to predict ion-binding properties and ion-dependent folding stabilities. PMID:20946803

Monoamine metabolites, iron induced seizures, and the anticonvulsant effect of tannins.

PubMed

Kabuto, H; Yokoi, I; Mori, A

1992-06-01

Intracortical injections of iron ions have been shown to induce recurrent seizures and epileptic discharges in the EEG. (-)-Epigallocatechin (EGC) and (-)-epigallocatechin-3-O-gallate (EGCG), isolated from green tea leaves, have been reported to prevent or diminish the occurrence of epileptic discharges induced by iron ions, and to inhibit catechol-O-methyltransferase. Iron ions significantly increased DOPAC and HVA levels in the intrastriatal perfusate 140 and 180 minutes, respectively, after injection. EGC and EGCG inhibited the increases induced by iron ions. Furthermore, EGCG decreased the HVA level in the perfusate 200 minutes after injection whether or not iron ions were injected. Iron ions had no effect on the 5-HIAA level, and EGC and EGCG raised it. These results suggest that formation of an epileptic focus induced by iron ions might be accompanied by activation of dopaminergic neurons, and that EGC and EGCG inhibit that hyperactivity.

Evidence for a glassy state in strongly driven carbon

DOE PAGES

Brown, C. R. D.; Gericke, D. O.; Cammarata, M.; ...

2014-06-09

Here, we report results of an experiment creating a transient, highly correlated carbon state using a combination of optical and x-ray lasers. Scattered x-rays reveal a highly ordered state with an electrostatic energy significantly exceeding the thermal energy of the ions. Strong Coulomb forces are predicted to induce nucleation into a crystalline ion structure within a few picoseconds. However, we observe no evidence of such phase transition after several tens of picoseconds but strong indications for an over-correlated fluid state. The experiment suggests a much slower nucleation and points to an intermediate glassy state where the ions are frozen closemore » to their original positions in the fluid.« less

First Principles Study on Topological-Phase Transition in Ferroelectric Oxides

NASA Astrophysics Data System (ADS)

Yamauchi, Kunihiko; Barone, Paolo; Picozzi, Silvia

Graphene is known as a 2D topological insulator with zero energy gap and Dirac cone. In this study, we theoretically designed a honeycomb structure of Au ions embedded in a ferroelectric host oxide, in order to exploit structural distortions to control topological properties. We show that the polar structural distortion induces the emergence of spin-valley coupling, together with a topological transition from a quantum spin-Hall insulating phase to a trivial band insulator. The phase transition also affects the Berry curvature and spin-valley selection rules. Analogously to graphene, the microscopic origin of this topological phase is ascribed to a spin-valley-sublattice coupling, which arises from the interplay between trigonal crystal field and an ``effective'' spin-orbit interaction due to virtual excitations between eg and t2g states of transition-metal ions.

High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries

DOE PAGES

Zhou, Yong-Ning; Yue, Ji-Li; Hu, Enyuan; ...

2016-08-08

Using fast time-resolved in situ X-ray diffraction, charge-rate dependent phase transition processes of layer structured cathode material LiNi 1/3Mn 1/3Co 1/3O 2 for lithium-ion batteries are studied. During first charge, intermediate phases emerge at high rates of 10C, 30C, and 60C, but not at low rates of 0.1C and 1C. These intermediate phases can be continuously observed during relaxation after the charging current is switched off. After half-way charging at high rate, sample studied by scanning transmission electron microscopy shows Li-rich and Li-poor phases' coexistence with tetrahedral occupation of Li in Li-poor phase. Also, the high rate induced overpotential ismore » thought to be the driving force for the formation of this intermediate Li-poor phase. The in situ quick X-ray absorption results show that the oxidation of Ni accelerates with increasing charging rate and the Ni 4+ state can be reached at the end of charge with 30C rate. Finally, these results give new insights in the understanding of the layered cathodes during high-rate charging.« less

Thermal annealing and transient electronic excitations induced interfacial and magnetic effects on Pt/Co/Pt trilayer

NASA Astrophysics Data System (ADS)

Sehdev, Neeru; Medwal, Rohit; Malik, Rakesh; Kandasami, Asokan; Kanjilal, Dinakar; Annapoorni, S.

2018-04-01

Present study investigates the importance of thermal annealing and transient electronic excitations (using 100 MeV oxygen ions) in assisting the interfacial atomic diffusion, alloy composition, and magnetic switching field distributions in Pt/Co/Pt stacked trilayer. X-ray diffraction analysis reveals that thermal annealing results in the formation of the face centered tetragonal L1°CoPt phase. The Rutherford back scattering spectra shows a trilayer structure for as-deposited and as-irradiated films. Interlayer mixing on the thermally annealed films further improves by electronic excitations produced by high energy ion irradiation. Magnetically hard face centered tetragonal CoPt alloy retains its hard phase after ion irradiation and reveals an enhancement in the structural ordering and magnetic stability. Enhancement in the homogeneity of alloy composition and its correlation with the magnetic switching field is evident from this study. A detailed investigation of the contributing parameters shows that the magnetic switching behaviour varies with the type of thermal annealing, transient electronic excitations of ion beams and combination of these processes.

2.7 MeV Ar11+ ion irradiation induced structural evolution in Lu2(Ti2-xLux)O7-x/2 pyrochlores

NASA Astrophysics Data System (ADS)

Yang, D. Y.; Liu, C. G.; Zhang, K. Q.; Xia, Y.; Chen, L. J.; Liu, H.; Li, Y. H.

2015-11-01

This paper aims to study the radiation effects of nonstoichiometric pyrochlore series Lu2(Ti2-xLux)O7-x/2 (x = 0-0.667). Polycrystalline Lu2(Ti2-xLux)O7-x/2 samples were irradiated with 2.7 MeV Ar11+ ions up to a fluence of 8 × 1014 ions/cm2. The irradiated samples were characterized using grazing incidence X-ray diffraction technique. The results reveal that Lu2(Ti2-xLux)O7-x/2 samples undergo significant amorphization and lattice swelling upon irradiation. Specifically, the amorphization process is predominantly driven by ballistic nuclear energy deposition of Ar11+ ions at this energy regime, which can be well described by a direct-impact/defect-stimulated model. Both the amorphization fraction and the relative variation of lattice parameter decrease with increasing x, showing a strong dependence on the chemical composition. The results are then discussed in the framework of the structural disorder and recovery ability from damage, applying an atomic layer model.

[Probabilistic calculations of biomolecule charge states that generate mass spectra of multiply charged ions].

PubMed

Raznikova, M O; Raznikov, V V

2015-01-01

In this work, information relating to charge states of biomolecule ions in solution obtained using the electrospray ionization mass spectrometry of different biopolymers is analyzed. The data analyses have mainly been carried out by solving an inverse problem of calculating the probabilities of retention of protons and other charge carriers by ionogenic groups of biomolecules with known primary structures. The approach is a new one and has no known to us analogues. A program titled "Decomposition" was developed and used to analyze the charge distribution of ions of native and denatured cytochrome c mass spectra. The possibility of splitting of the charge-state distribution of albumin into normal components, which likely corresponds to various conformational states of the biomolecule, has been demonstrated. The applicability criterion for using previously described method of decomposition of multidimensional charge-state distributions with two charge carriers, e.g., a proton and a sodium ion, to characterize the spatial structure of biopolymers in solution has been formulated. In contrast to known mass-spectrometric approaches, this method does not require the use of enzymatic hydrolysis or collision-induced dissociation of the biopolymers.

Whiskers growth and self-healing in Ti-based metallic glasses during ion irradiation

NASA Astrophysics Data System (ADS)

Zhang, Kun; Hu, Zheng; Zhao, Ziqiang; Wei, Bingchen; Li, Yansen; Wei, Yuhang

2018-04-01

Ti-based metallic glasses were subjected to a 20 MeV Cl4+ ion radiation under liquid-nitrogen cooling. Their responses, as well as effects of the electronic excitation and nucleus-nucleus collision were evaluated. The collision cascade during irradiation typically changes the structure by increasing the liquid-like zone/cluster, or the content of the free volume. However, along the ion incident depth, the structure change is inhomogeneous. Numerous whiskers appear and aggregate on the side of the irradiation surface, which are several micrometers away from the edge. This corresponds with the maximum collision depth obtained by the Monte Carlo simulation, where nuclear loss plays a dominant role. Moreover, the liquid-like zone continually forms, which add to the whiskers growth and subsequent self-healing. Results suggest that the irradiation-induced local shear stress combines with the well-localized liquid-like zone results in the observed phenomena. This study demonstrates that metallic glasses have high morphological instability under ion irradiation, which assets can pave new paths for their further applications.

Collision-induced dissociation of diazirine-labeled peptide ions. Evidence for Brønsted-acid assisted elimination of nitrogen.

PubMed

Marek, Aleš; Tureček, František

2014-05-01

Gas-phase dissociations were investigated for several peptide ions containing the Gly-Leu* N-terminal motif where Leu* was a modified norleucine residue containing the photolabile diazirine ring. Collisional activation of gas-phase peptide cations resulted in facile N₂ elimination that competed with backbone dissociations. A free lysine ammonium group can act as a Brønsted acid to facilitate N₂ elimination. This dissociation was accompanied by insertion of a lysine proton in the side chain of the photoleucine residue, as established by deuterium labeling and gas-phase sequencing of the products. Electron structure calculations were used to provide structures and energies of reactants, intermediates, and transition states for Gly-Leu*-Gly-Gly-Lys amide ions that were combined with RRKM calculations of unimolecular rate constants. The calculations indicated that Brønsted acid-catalyzed eliminations were kinetically preferred over direct loss of N₂ from the diazirine ring. Mechanisms are proposed to explain the proton-initiated reactions and discuss the reaction products. The non-catalyzed diazirine ring cleavage and N₂ loss is proposed as a thermometer dissociation for peptide ion dissociations.

Spatial Studies of Ion Beams in an Expanding Plasma

NASA Astrophysics Data System (ADS)

Aguirre, Evan; Good, Timothy; Scime, Earl; Thompson, Derek

2017-10-01

We report spatially resolved perpendicular and parallel ion velocity distribution function (IVDF) measurements in an expanding argon helicon plasma. The parallel IVDFs, obtained through laser induced fluorescence (LIF), show an ion beam with v 8 km/s flowing downstream that is confined to the center of the discharge. The ion beam is confined to within a few centimeters radially and is measurable for tens of centimeters axially before the LIF signal fades, likely a result of metastable quenching of the beam ions. The axial ion beam velocity slows in agreement with collisional processes. The perpendicular IVDFs show an ion population with a radially outward flow that increases with radial location. The DC electric field, electron temperature, and the plasma density in the double layer plume are all consistent with magnetic field aligned structures. The upstream and downstream electric field measurements show clear evidence of an ion hole that maps along the magnetic field at the edge of the plasma. Current theories and simulations of double layers, which are one-dimensional, completely miss these critically important two-dimensional features.

Molecular dynamics simulation of Bu4N+ in dimethylformamide: Solvation-induced volume changes

NASA Astrophysics Data System (ADS)

Kiselev, M. G.; Safonova, L. P.

2011-06-01

The structure of the Bu4N+-dimethylformamide system in the condensed and gas phases was studied by molecular dynamics simulation and quantum-chemical calculations. The calculation results were used to reveal the role played by steric effects in the volumetric characteristics of ion solvation.

High fluence swift heavy ion structure modification of the SiO2/Si interface and gate insulator in 65 nm MOSFETs

NASA Astrophysics Data System (ADS)

Ma, Yao; Gao, Bo; Gong, Min; Willis, Maureen; Yang, Zhimei; Guan, Mingyue; Li, Yun

2017-04-01

In this work, a study of the structure modification, induced by high fluence swift heavy ion radiation, of the SiO2/Si structures and gate oxide interface in commercial 65 nm MOSFETs is performed. A key and novel point in this study is the specific use of the transmission electron microscopy (TEM) technique instead of the conventional atomic force microscope (AFM) or scanning electron microscope (SEM) techniques which are typically performed following the chemical etching of the sample to observe the changes in the structure. Using this method we show that after radiation, the appearance of a clearly visible thin layer between the SiO2 and Si is observed presenting as a variation in the TEM intensity at the interface of the two materials. Through measuring the EDX line scans we reveal that the Si:O ratio changed and that this change can be attributed to the migration of the Si towards interface after the Si-O bond is destroyed by the swift heavy ions. For the 65 nm MOSFET sample, the silicon substrate, the SiON insulator and the poly-silicon gate interfaces become blurred under the same irradiation conditions.

Large and stable reversible lithium-ion storages from mesoporous SnO2 nanosheets with ultralong lifespan over 1000 cycles

NASA Astrophysics Data System (ADS)

Zhang, Xiao; Jiang, Bin; Guo, Jinxue; Xie, Yaping; Tang, Lin

2014-12-01

The major challenge to promote the commercialization of SnO2 anode materials is to construct unique structures and/or composites that could alleviate the volume effect and extend the lifespan. This study develops an efficient synthetic solution for the preparation of mesoporous SnO2 nanosheets, which involves an evaporation-induced selfassembly process and the following thermal treatment. Surfactant F127 is used as the soft template to form abundant cores. The as-prepared sample intrinsically inherits flexible sheet-like structure and porous features, as characterized with XRD, SEM, TEM and BET techniques. Based on these combining structural benefits, the sample is utilized as anode materials for lithium-ion batteries and exhibits excellent Li+ storage performance such as large and stable reversible capacity, good rate capability, and especially the outstanding durable cycling life of over 1000 cycles, which meets the demands of practical applications. The structural changes of SnO2 nanosheets are observed from the decomposed electrodes after different electrochemical cycles. Moreover, this synthesis strategy may offer an alternative and universal approach for synthesis of other transitional metal oxides or their binary composites as high-performance anode materials for lithium-ion batteries.

Detwinning through migration of twin boundaries in nanotwinned Cu films under in situ ion irradiation

PubMed Central

Du, Jinlong; Wu, Zaoming; Fu, Engang; Liang, Yanxiang; Wang, Xingjun; Wang, Peipei; Yu, Kaiyuan; Ding, Xiangdong; Li, Meimei; Kirk, Marquis

2018-01-01

Abstract The mechanism of radiation-induced detwinning is different from that of deformation detwinning as the former is dominated by supersaturated radiation-induced defects while the latter is usually triggered by global stress. In situ Kr ion irradiation was performed to study the detwinning mechanism of nanotwinned Cu films with various twin thicknesses. Two types of incoherent twin boundaries (ITBs), so-called fixed ITBs and free ITBs, are characterized based on their structural features, and the difference in their migration behavior is investigated. It is observed that detwinning during radiation is attributed to the frequent migration of free ITBs, while the migration of fixed ITBs is absent. Statistics shows that the migration distance of free ITBs is thickness and dose dependent. Potential migration mechanisms are discussed. PMID:29535796

Detwinning through migration of twin boundaries in nanotwinned Cu films under in situ ion irradiation.

PubMed

Du, Jinlong; Wu, Zaoming; Fu, Engang; Liang, Yanxiang; Wang, Xingjun; Wang, Peipei; Yu, Kaiyuan; Ding, Xiangdong; Li, Meimei; Kirk, Marquis

2018-01-01

The mechanism of radiation-induced detwinning is different from that of deformation detwinning as the former is dominated by supersaturated radiation-induced defects while the latter is usually triggered by global stress. In situ Kr ion irradiation was performed to study the detwinning mechanism of nanotwinned Cu films with various twin thicknesses. Two types of incoherent twin boundaries (ITBs), so-called fixed ITBs and free ITBs, are characterized based on their structural features, and the difference in their migration behavior is investigated. It is observed that detwinning during radiation is attributed to the frequent migration of free ITBs, while the migration of fixed ITBs is absent. Statistics shows that the migration distance of free ITBs is thickness and dose dependent. Potential migration mechanisms are discussed.

Investigating lithium-ion battery materials during overcharge-induced thermal runaway: an operando and multi-scale X-ray CT study.

PubMed

Finegan, Donal P; Scheel, Mario; Robinson, James B; Tjaden, Bernhard; Di Michiel, Marco; Hinds, Gareth; Brett, Dan J L; Shearing, Paul R

2016-11-16

Catastrophic failure of lithium-ion batteries occurs across multiple length scales and over very short time periods. A combination of high-speed operando tomography, thermal imaging and electrochemical measurements is used to probe the degradation mechanisms leading up to overcharge-induced thermal runaway of a LiCoO 2 pouch cell, through its interrelated dynamic structural, thermal and electrical responses. Failure mechanisms across multiple length scales are explored using a post-mortem multi-scale tomography approach, revealing significant morphological and phase changes in the LiCoO 2 electrode microstructure and location dependent degradation. This combined operando and multi-scale X-ray computed tomography (CT) technique is demonstrated as a comprehensive approach to understanding battery degradation and failure.

Negative differential resistance effect induced by metal ion implantation in SiO2 film for multilevel RRAM application

NASA Astrophysics Data System (ADS)

Wu, Facai; Si, Shuyao; Shi, Tuo; Zhao, Xiaolong; Liu, Qi; Liao, Lei; Lv, Hangbing; Long, Shibing; Liu, Ming

2018-02-01

Pt/SiO2:metal nanoparticles/Pt sandwich structure is fabricated with the method of metal ion (Ag) implantation. The device exhibits multilevel storage with appropriate R off/R on ratio, good endurance and retention properties. Based on transmission electron microscopy and energy dispersive spectrometer analysis, we confirm that Pt nanoparticles are spurted into SiO2 film from Pt bottom electrode by Ag implantation; during electroforming, the local electric field can be enhanced by these Pt nanoparticles, meanwhile the Ag nanoparticles constantly migrate toward the Pt nanoparticles. The implantation induced nanoparticles act as trap sites in the resistive switching layer and play critical roles in the multilevel storage, which is evidenced by the negative differential resistance effect in the current-voltage (I-V) measurements.

Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

DOE PAGES

Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan; ...

2014-11-18

Through a systematic study of lithium molybdenum trioxide (Li 2MoO 3), a new ‘unit cell breathing’ mechanism is introduced based on both crystal and electronic structural changes of transition metal oxide cathode materials during charge–discharge: For widely used LiMO 2 (M = Co, Ni, Mn), lattice parameters, a and b, contracts during charge. However, for Li 2MoO 3, such changes are in opposite directions. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of M–M bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking M–O asmore » controlling factor in ‘normal’ materials. The cation mixing caused by migration of Mo ions at higher oxidation state provides the benefits of reducing the c expansion range in early stage of charging and suppressing the structure collapse at high voltage charge. These results open a new strategy for designing and engineering layered cathode materials for high energy density lithium-ion batteries.« less

Structure and transport mechanism of the sodium/proton antiporter MjNhaP1

PubMed Central

Paulino, Cristina; Wöhlert, David; Kapotova, Ekaterina; Yildiz, Özkan; Kühlbrandt, Werner

2014-01-01

Sodium/proton antiporters are essential for sodium and pH homeostasis and play a major role in human health and disease. We determined the structures of the archaeal sodium/proton antiporter MjNhaP1 in two complementary states. The inward-open state was obtained by x-ray crystallography in the presence of sodium at pH 8, where the transporter is highly active. The outward-open state was obtained by electron crystallography without sodium at pH 4, where MjNhaP1 is inactive. Comparison of both structures reveals a 7° tilt of the 6 helix bundle. 22Na+ uptake measurements indicate non-cooperative transport with an activity maximum at pH 7.5. We conclude that binding of a Na+ ion from the outside induces helix movements that close the extracellular cavity, open the cytoplasmic funnel, and result in a ∼5 Å vertical relocation of the ion binding site to release the substrate ion into the cytoplasm. DOI: http://dx.doi.org/10.7554/eLife.03583.001 PMID:25426803

Tunable self-organization of nanocomposite multilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, C. Q.; Pei, Y. T.; Shaha, K. P.

In this letter we report the controlled growth and microstructural evolution of self-assembled nanocomposite multilayers that are induced by surface ion-impingement. The nanoscale structures together with chemical composition, especially at the growing front, have been investigated with high-resolution transmission electron microscopy. Concurrent ion impingement of growing films produces an amorphous capping layer 3 nm in thickness where spatially modulated phase separation is initiated. It is shown that the modulation of multilayers as controlled by the self-organization of nanocrystallites below the capping layer, can be tuned through the entire film.

Synthesis of nanodimensional orthorhombic SnO2 thin films

NASA Astrophysics Data System (ADS)

Kondkar, V.; Rukade, D.; Kanjilal, D.; Bhattacharyya, V.

2018-04-01

Amorphous thin films of SnO2 are irradiated by swift heavy ions at two different fluences. Unirradiated as well as irradiated films are characterized by glancing angle X-ray diffraction (GAXRD), UV-Vis spectroscopy and atomic force microscopy (AFM). GAXRD study reveals formation of orthorhombic nanophases of SnO2. Nanophase formation is also confirmed by the quantum size effect manifested by blue shift in terms of increase in band gap energy. The size and shape of the irradiation induced surface structures depend on ion fluence.

Femtosecond manipulation of spins, charges, and ions in nanostructures, thin films, and surfaces

PubMed Central

Carbone, F.; Hengsberger, M.; Castiglioni, L.; Osterwalder, J.

2017-01-01

Modern ultrafast techniques provide new insights into the dynamics of ions, charges, and spins in photoexcited nanostructures. In this review, we describe the use of time-resolved electron-based methods to address specific questions such as the ordering properties of self-assembled nanoparticles supracrystals, the interplay between electronic and structural dynamics in surfaces and adsorbate layers, the light-induced control of collective electronic modes in nanowires and thin films, and the real-space/real-time evolution of the skyrmion lattice in topological magnets. PMID:29308416

FTIR Study of ATP-Induced Changes in Na+/K+-ATPase from Duck Supraorbital Glands

PubMed Central

Pratap, Promod R.; Dediu, Oana; Nienhaus, G. Ulrich

2003-01-01

The Na+/K+-ATPase uses energy from the hydrolysis of ATP to pump Na+ ions out of and K+ ions into the cell. ATP-induced conformational changes in the protein have been examined in the Na+/K+-ATPase isolated from duck supraorbital salt glands using Fourier transform infrared spectroscopy. Both standard transmission and attenuated total internal reflection sample geometries have been employed. Under transmission conditions, enzyme at 75 mg/ml was incubated with dimethoxybenzoin-caged ATP. ATP was released by flashing with a UV laser pulse at 355 nm, which resulted in a large change in the amide I band. The absorbance at 1659 cm−1 decreased with a concomitant increase in the absorbance at 1620 cm−1. These changes are consistent with a partial conversion of protein secondary structure from α-helix to β-sheet. The changes were ∼8% of the total absorbance, much larger than those seen with other P-type ATPases. Using attenuated total internal reflection Fourier transform infrared spectroscopy, the decrease in absorbance at ∼1650 cm−1 was titrated with ATP, and the titration midpoint K0.5 was determined under different ionic conditions. In the presence of metal ions (Na+, Na+ and K+, or Mg2+), K0.5 was on the order of a few μM. In the absence of these ions, K0.5 was an order of magnitude lower (0.1 μM), indicating a higher apparent affinity. This effect suggests that the equilibrium for the ATP-induced conformational changes is dependent on the presence of metal ions. PMID:14645062

Swift heavy ion-beam induced amorphization and recrystallization of yttrium iron garnet.

PubMed

Costantini, Jean-Marc; Miro, Sandrine; Beuneu, François; Toulemonde, Marcel

2015-12-16

Pure and (Ca and Si)-substituted yttrium iron garnet (Y3Fe5O12 or YIG) epitaxial layers and amorphous films on gadolinium gallium garnet (Gd3Ga5O12, or GGG) single crystal substrates were irradiated by 50 MeV (32)Si and 50 MeV (or 60 MeV) (63)Cu ions for electronic stopping powers larger than the threshold value (~4 MeV μm(-1)) for amorphous track formation in YIG crystals. Conductivity data of crystalline samples in a broad ion fluence range (10(11)-10(16) cm(-2)) are modeled with a set of rate equations corresponding to the amorphization and recrystallization induced in ion tracks by electronic excitations. The data for amorphous layers confirm that a recrystallization process takes place above ~10(14) cm(-2). Cross sections for both processes deduced from this analysis are discussed in comparison to previous determinations with reference to the inelastic thermal-spike model of track formation. Micro-Raman spectroscopy was also used to follow the related structural modifications. Raman spectra show the progressive vanishing and randomization of crystal phonon modes in relation to the ion-induced damage. For crystalline samples irradiated at high fluences (⩾10(14) cm(-2)), only two prominent broad bands remain like for amorphous films, thereby reflecting the phonon density of states of the disordered solid, regardless of samples and irradiation conditions. The main band peaked at ~660 cm(-1) is assigned to vibration modes of randomized bonds in tetrahedral (FeO4) units.

Experimental Retrieval of Target Structure Information from Laser-Induced Rescattered Photoelectron Momentum Distributions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okunishi, M.; Pruemper, G.; Shimada, K.

We have measured two-dimensional photoelectron momentum spectra of Ne, Ar, and Xe generated by 800-nm, 100-fs laser pulses and succeeded in identifying the spectral ridge region (back-rescattered ridges) which marks the location of the returning electrons that have been backscattered at their maximum kinetic energies. We demonstrate that the structural information, in particular the differential elastic scattering cross sections of the target ion by free electrons, can be accurately extracted from the intensity distributions of photoelectrons on the ridges, thus effecting a first step toward laser-induced self-imaging of the target, with unprecedented spatial and temporal resolutions.

A comparative study on low-energy ion beam and neutralized beam modifications of naked DNA and biological effect on mutation

NASA Astrophysics Data System (ADS)

Sarapirom, S.; Thongkumkoon, P.; Prakrajang, K.; Anuntalabhochai, S.; Yu, L. D.

2012-02-01

DNA conformation change or damage induced by low-energy ion irradiation has been of great interest owing to research developments in ion beam biotechnology and ion beam application in biomedicine. Mechanisms involved in the induction of DNA damage may account for effect from implanting ion charge. In order to check this effect, we used both ion beam and neutralized beam at keV energy to bombard naked DNA. Argon or nitrogen ion beam was generated and extracted from a radiofrequency (RF) ion source and neutralized by microwave-driven plasma in the beam path. Plasmid DNA pGFP samples were irradiated with the ion or neutralized beam in vacuum, followed by gel electrophoresis to observe changes in the DNA conformations. It was revealed that the ion charge played a certain role in inducing DNA conformation change. The subsequent DNA transfer into bacteria Escherichia coli ( E. coli) for mutation analysis indicated that the charged ion beam induced DNA change had high potential in mutation induction while neutralized beam did not. The intrinsic reason was attributed to additional DNA deformation and contortion caused by ion charge exchange effect so that the ion beam induced DNA damage could hardly be completely repaired, whereas the neutralized beam induced DNA change could be more easily recoverable owing to absence of the additional DNA deformation and contortion.

Mesh-structured N-doped graphene@Sb2Se3 hybrids as an anode for large capacity sodium-ion batteries.

PubMed

Zhao, Wenxi; Li, Chang Ming

2017-02-15

A mesh-structured N-doped graphene@Sb 2 Se 3 (NGS) hybrid was one-pot prepared to realize N-doping, nanostructuring and hybridization for a sodium-ion battery anode to deliver much larger reversible specific capacity, faster interfacial electron transfer rate, better ionic and electronic transport, higher rate performance and longer cycle life stability in comparison to the plain Sb 2 Se 3 one. The better performance is ascribed to the unique intertwined porous mash-like structure associated with a strong synergistic effect of N-doped graphene for dramatic improvement of electronic and ionic conductivity by the unique porous structure, the specific capacity of graphene from N doping and fast interfacial electron transfer rate by N-doping induced surface effect and the structure-shortening insertion/desertion pathway of Na + . The detail electrochemical process on the NGS electrode is proposed and analyzed in terms of the experimental results. Copyright © 2016 Elsevier Inc. All rights reserved.

Recent advances on the understanding of structural and composition evolution of LMR cathodes for Li-ion batteries

DOE PAGES

Yan, Pengfei; Zheng, Jianming; Xiao, Jie; ...

2015-06-08

Lithium-rich, magnesium-rich (LMR) cathode materials have been regarded as one of the very promising cathodes for Li-ion battery applications. However, their practical application is still limited by several challenges, especially by their limited electrochemical stability rate capability. In this work, we present recent progresses on the understanding of the structural and composition evolution of LMR cathode materials with emphasis being placed on the correlation between structural/chemical evolution and electrochemical properties. In particular, using Li [Li 0.2Ni 0.2Mn 0.6O 2 as a typical example, we clearly illustrate the structural characteristics of the pristine materials and their dependence on the materials processingmore » history, cycling induced structural degradation/chemical partition and their correlation with degradation of electrochemical performance. The fundamental understanding obtained in this work may also guide the design and preparation of new cathode materials based on ternary system of transitional metal oxide.« less

Effects of 200 keV argon ions irradiation on microstructural properties of titanium nitride films

NASA Astrophysics Data System (ADS)

Popović, M.; Novaković, M.; Šiljegović, M.; Bibić, N.

2012-05-01

This paper reports on a study of microstructrual changes in TiN/Si bilayers due to 200 keV Ar+ ions irradiation at room temperature. The 240 nm TiN/Si bilayers were prepared by d.c. reactive sputtering on crystalline Si (1 0 0) substrates. The TiN films were deposited at the substrate temperature of 150 °C. After deposition the TiN/Si bilayers were irradiated to the fluences of 5 × 1015 and 2 × 1016 ions/cm2. The structural changes induced by ion irradiation in the TiN/Si bilayers were analyzed by Rutherford Backscattering Spectroscopy (RBS), X-ray diffraction analyses (XRD) and Transmission Electron Microscopy (TEM). The irradiations caused the microstructrual changes in TiN layers, but no amorphization even at the highest argon fluence of 2 × 1016 ions/cm2. It is also observed that the mean crystallite size decreases with the increasing ion fluence.

Fragmentation pathways of O-alkyl methylphosphonothionocyanidates in the gas phase: toward unambiguous structural characterization of chemicals in the Chemical Weapons Convention framework.

PubMed

Saeidian, Hamid; Babri, Mehran; Ashrafi, Davood; Sarabadani, Mansour; Naseri, Mohammad Taghi

2013-08-01

The electron-impact (EI) mass spectra of a series of O-alkyl methylphosphonothionocyanidates were studied for Chemical Weapons Convention (CWC) purposes. General EI fragmentation pathways were constructed and discussed, and collision-induced dissociation studies of the major EI ions were performed to confirm proposed fragment structures by analyzing fragment ions of deuterated analogs and by use of density functional theory (DFT) calculations. Thiono-thiolo rearrangement, McLafferty-type rearrangement, and a previously unknown intramolecular electrophilic aromatic substitution reaction were observed and confirmed. The study also focused on differentiation of isomeric compounds. Retention indices for all compounds, and an electrophilicity index for several compounds, are reported and interpreted.

Atomistic structures of nano-engineered SiC and radiation-induced amorphization resistance

NASA Astrophysics Data System (ADS)

Imada, Kenta; Ishimaru, Manabu; Sato, Kazuhisa; Xue, Haizhou; Zhang, Yanwen; Shannon, Steven; Weber, William J.

2015-10-01

Nano-engineered 3C-SiC thin films, which possess columnar structures with high-density stacking faults and twins, were irradiated with 2 MeV Si ions at cryogenic and room temperatures. From cross-sectional transmission electron microscopy observations in combination with Monte Carlo simulations based on the Stopping and Range of Ions in Matter code, it was found that their amorphization resistance is six times greater than bulk crystalline SiC at room temperature. High-angle bright-field images taken by spherical aberration corrected scanning transmission electron microscopy revealed that the distortion of atomic configurations is localized near the stacking faults. The resultant strain field probably contributes to the enhancement of radiation tolerance of this material.

Properties of arsenic-implanted Hg1-xCdxTe MBE films

NASA Astrophysics Data System (ADS)

Izhnin, Igor I.; Voitsekhovskii, Alexandr V.; Korotaev, Alexandr G.; Fitsych, Olena I.; Bonchyk, Oleksandr Yu.; Savytskyy, Hrygory V.; Mynbaev, Karim D.; Varavin, Vasilii S.; Dvoretsky, Sergey A.; Yakushev, Maxim V.; Jakiela, Rafal; Trzyna, Malgorzata

2017-01-01

Defect structure of arsenic-implanted Hg1-xCdxTe films (x=0.23-0.30) grown with molecular-beam epitaxy on Si substrates was investigated with the use of optical methods and by studying the electrical properties of the films. The structural perfection of the films remained higher after implantation with more energetic arsenic ions (350 keV vs 190 keV). 100%-activation of implanted ions as a result of post-implantation annealing was achieved, as well as the effective removal of radiation-induced donor defects. In some samples, however, activation of acceptor-like defects not related to mercury vacancies as a result of annealing was observed, possibly related to the effect of the substrate.

Effect of He+ fluence on surface morphology and ion-irradiation induced defect evolution in 7075 aluminum alloys

NASA Astrophysics Data System (ADS)

Ni, Kai; Ma, Qian; Wan, Hao; Yang, Bin; Ge, Junjie; Zhang, Lingyu; Si, Naichao

2018-02-01

The evolution of microstructure for 7075 aluminum alloys with 50 Kev helium ions irradiation were studied by using optical microscopy (OM), scanning electron microscopy (SEM), x-ray diffraction (XRD) and transmission electron microscopy (TEM). The fluences of 1 × 1015, 1 × 1016 and 1 × 1017 ions cm-2 were selected, and irradiation experiments were conducted at room temperatures. The transmission process of He+ ions was simulated by using SRIM software, including distribution of ion ranges, energy losses and atomic displacements. Experimental results show that irradiated pits and micro-cracks were observed on irradiation sample surface, and the size of constituent particles (not including Mg2Si) decreased with the increasing dose. The x-ray diffraction results of the pair of peaks is better resolved in irradiated samples might indicate that the stressed structure consequence due to crystal defects (vacancies and interstitials) after He+ implantation. TEM observation indicated that the density of MgZn2 phase was significantly reduced after helium ion irradiation which is harmful to strength. Besides, the development of compressive stress produced a large amount of dislocation defects in the 1015 ions cm-2 sample. Moreover, higher fluence irradiation produced more dislocations in sample. At fluence of 1016 ions cm-2, dislocation wall formed by dislocation slip and aggregation in the interior of grains, leading to the refinement of these grains. As fluence increased to 1017 ions cm-2, dislocation loops were observed in pinned dislocation. Moreover, dislocation as effective defect sink, irradiation-induced vacancy defects aggregated to these sinks, and resulted in the formation of helium bubbles in dislocation.

Ion-beam-induced magnetic transformation of CO-stabilized fcc Fe films on Cu(100)

NASA Astrophysics Data System (ADS)

Shah Zaman, Sameena; Oßmer, Hinnerk; Jonner, Jakub; Novotný, Zbyněk; Buchsbaum, Andreas; Schmid, Michael; Varga, Peter

2010-12-01

We have grown 22-ML-thick Fe films on a Cu(100) single crystal. The films were stabilized in the face-centered-cubic (fcc) γ phase by adsorption of carbon monoxide during growth, preventing the transformation to the body-centered-cubic (bcc) α phase. A structural transformation of these films from fcc to bcc can be induced by Ar+ ion irradiation. Scanning-tunneling microscopy images show the nucleation of bcc crystallites, which grow with increasing Ar+ ion dose and eventually result in complete transformation of the film to bcc. Surface magneto-optic Kerr effect measurements confirm the transformation of the Fe film from paramagnetic (fcc) to ferromagnetic (bcc) with an in-plane easy axis. The transformation can also be observed by low-energy electron diffraction. We find only very few nucleation sites of the bcc phase and argue that nucleation of the bcc phase happens under special circumstances during resolidification of the molten iron in the thermal spike after ion impact. Intermixing with the Cu substrate impedes the transformation. We also demonstrate the transformation of films coated with Au to protect them from oxidation at ambient conditions.

High-performance Supercapacitors Based on Electrochemical-induced Vertical-aligned Carbon Nanotubes and Polyaniline Nanocomposite Electrodes

NASA Astrophysics Data System (ADS)

Wu, Guan; Tan, Pengfeng; Wang, Dongxing; Li, Zhe; Peng, Lu; Hu, Ying; Wang, Caifeng; Zhu, Wei; Chen, Su; Chen, Wei

2017-03-01

Supercapacitors, which store electrical energy through reversible ion on the surface of conductive electrodes have gained enormous attention for variously portable energy storage devices. Since the capacitive performance is mainly determined by the structural and electrochemical properties of electrodes, the electrodes become more crucial to higher performance. However, due to the disordered microstructure and low electrochemical activity of electrode for ion tortuous migration and accumulation, the supercapacitors present relatively low capacitance and energy density. Here we report a high-performance supercapacitor based on polyaniline/vertical-aligned carbon nanotubes (PANI/VA-CNTs) nanocomposite electrodes where the vertical-aligned-structure is formed by the electrochemical-induction (0.75 V). The supercapacitor displays large specific capacitance of 403.3 F g-1, which is 6 times higher than disordered CNTs in HClO4 electrolyte. Additionally, the supercapacitor can also present high specific capacitance (314.6 F g-1), excellent cycling stability (90.2% retention after 3000 cycles at 4 A g-1) and high energy density (98.1 Wh kg-1) in EMIBF4 organic electrolyte. The key to high-performance lies in the vertical-aligned-structure providing direct path channel for ion faster diffusion and high electrochemical capacitance of polyaniline for ion more accommodation.

Electrochemical-mechanical coupling in composite planar structures that integrate flow channels and ion-conducting membranes

DOE PAGES

Euser, Bryan Jeffry; Zhu, Huayang; Berger, John; ...

2017-01-01

Ceramic oxygen-transport membranes, such as the doped perovskite La 0.6Sr 0.4Co 0.8Fe 0.2O 3-δ(LSCF6482) considered in the present paper, are effective in applications such as air separation. The present paper considers a planar configuration that is composed of a thin (order tens of microns) ion-transport membrane, a relatively thick (order millimeter) porous-ceramic support structure, and millimeter-scale oxygen-collection flow channels. The lattice-scale strain associated with charged defects (oxygen vacancies and small polarons) within ion-transport membranes causes macroscopic stress that could distort or damage the assembly. The modeling approach is based on an extended twodimensional Nernst–Planck–Poisson (NPP) formulation that is developed andmore » applied to evaluate the effects of chemically induced stress within a planar oxygen-separation assembly. The computational model predicts two-dimensional distributions of steady-state defect concentrations, electrostatic potentials, and stress. Parameter studies consider the effects of support-membrane dimensions, materials mechanical properties, and operating conditions. Although the stress is found to have a negligible influence on the defect transport, the defect transport is found to significantly affect the stress distributions. Such results can play important roles in the design and development of planar ion-transport membranes and their support structures.« less

High-performance Supercapacitors Based on Electrochemical-induced Vertical-aligned Carbon Nanotubes and Polyaniline Nanocomposite Electrodes.

PubMed

Wu, Guan; Tan, Pengfeng; Wang, Dongxing; Li, Zhe; Peng, Lu; Hu, Ying; Wang, Caifeng; Zhu, Wei; Chen, Su; Chen, Wei

2017-03-08

Supercapacitors, which store electrical energy through reversible ion on the surface of conductive electrodes have gained enormous attention for variously portable energy storage devices. Since the capacitive performance is mainly determined by the structural and electrochemical properties of electrodes, the electrodes become more crucial to higher performance. However, due to the disordered microstructure and low electrochemical activity of electrode for ion tortuous migration and accumulation, the supercapacitors present relatively low capacitance and energy density. Here we report a high-performance supercapacitor based on polyaniline/vertical-aligned carbon nanotubes (PANI/VA-CNTs) nanocomposite electrodes where the vertical-aligned-structure is formed by the electrochemical-induction (0.75 V). The supercapacitor displays large specific capacitance of 403.3 F g -1 , which is 6 times higher than disordered CNTs in HClO 4 electrolyte. Additionally, the supercapacitor can also present high specific capacitance (314.6 F g -1 ), excellent cycling stability (90.2% retention after 3000 cycles at 4 A g -1 ) and high energy density (98.1 Wh kg -1 ) in EMIBF 4 organic electrolyte. The key to high-performance lies in the vertical-aligned-structure providing direct path channel for ion faster diffusion and high electrochemical capacitance of polyaniline for ion more accommodation.

High-performance Supercapacitors Based on Electrochemical-induced Vertical-aligned Carbon Nanotubes and Polyaniline Nanocomposite Electrodes

PubMed Central

Wu, Guan; Tan, Pengfeng; Wang, Dongxing; Li, Zhe; Peng, Lu; Hu, Ying; Wang, Caifeng; Zhu, Wei; Chen, Su; Chen, Wei

2017-01-01

Supercapacitors, which store electrical energy through reversible ion on the surface of conductive electrodes have gained enormous attention for variously portable energy storage devices. Since the capacitive performance is mainly determined by the structural and electrochemical properties of electrodes, the electrodes become more crucial to higher performance. However, due to the disordered microstructure and low electrochemical activity of electrode for ion tortuous migration and accumulation, the supercapacitors present relatively low capacitance and energy density. Here we report a high-performance supercapacitor based on polyaniline/vertical-aligned carbon nanotubes (PANI/VA-CNTs) nanocomposite electrodes where the vertical-aligned-structure is formed by the electrochemical-induction (0.75 V). The supercapacitor displays large specific capacitance of 403.3 F g−1, which is 6 times higher than disordered CNTs in HClO4 electrolyte. Additionally, the supercapacitor can also present high specific capacitance (314.6 F g−1), excellent cycling stability (90.2% retention after 3000 cycles at 4 A g−1) and high energy density (98.1 Wh kg−1) in EMIBF4 organic electrolyte. The key to high-performance lies in the vertical-aligned-structure providing direct path channel for ion faster diffusion and high electrochemical capacitance of polyaniline for ion more accommodation. PMID:28272474

Recrystallization-Induced Surface Cracks of Carbon Ions Irradiated 6H-SiC after Annealing

PubMed Central

Ye, Chao; Ran, Guang; Zhou, Wei; Shen, Qiang; Feng, Qijie; Lin, Jianxin

2017-01-01

Single crystal 6H-SiC wafers with 4° off-axis [0001] orientation were irradiated with carbon ions and then annealed at 900 °C for different time periods. The microstructure and surface morphology of these samples were investigated by grazing incidence X-ray diffraction (GIXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Ion irradiation induced SiC amorphization, but the surface was smooth and did not have special structures. During the annealing process, the amorphous SiC was recrystallized to form columnar crystals that had a large amount of twin structures. The longer the annealing time was, the greater the amount of recrystallized SiC would be. The recrystallization volume fraction was accorded with the law of the Johnson–Mehl–Avrami equation. The surface morphology consisted of tiny pieces with an average width of approximately 30 nm in the annealed SiC. The volume shrinkage of irradiated SiC layer and the anisotropy of newly born crystals during annealing process produced internal stress and then induced not only a large number of dislocation walls in the non-irradiated layer but also the initiation and propagation of the cracks. The direction of dislocation walls was perpendicular to the growth direction of the columnar crystal. The longer the annealing time was, the larger the length and width of the formed crack would be. A quantitative model of the crack growth was provided to calculate the length and width of the cracks at a given annealing time. PMID:29068408

Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization

NASA Astrophysics Data System (ADS)

Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P.

2016-10-01

The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting.

Compositional and structural analysis of nitrogen incorporated and ion implanted diamond thin films

NASA Astrophysics Data System (ADS)

Garratt, Elias James

Significant progress in area of nano-structured thin film systems has taken place in recent decades. In particular, diamond thin film systems are being widely studied for their wear resistant, optical and electronic properties. Of the various methods researchers use to modify the structure of such films, three techniques in particular are of interest due to their versatility: modification of the growth atmosphere, growth on metalized substrates, providing an interfacial layer, and modification through post-growth ion implantation. The aim of this study is to investigate the effects each has to the structure and composition of elements. Different techniques are applied in each section; nitrogen gas dilution in a microwave plasma CVD system, diamond deposition on a metal interfacial layer and ion implantation in thin nanocrystalline diamond film. The forms of nanocrystalline diamond film resulting from such modifications are investigated using advanced spectroscopic and spectrometric techniques, as well as mechanical testing and surface mapping. The impact of these characterizations will provide valuable perspective to researchers in materials science. Understanding the changes to the structure and properties of this class of thin films, which can be induced through various mechanisms, will allow future researchers to refine these films towards technological applications in areas of hard coatings, electronics and photonics.

High yield antibiotic producing mutants of Streptomyces erythreus induced by low energy ion implantation

NASA Astrophysics Data System (ADS)

Yu, Chen; Zhixin, Lin; Zuyao, Zou; Feng, Zhang; Duo, Liu; Xianghuai, Liu; Jianzhong, Tang; Weimin, Zhu; Bo, Huang

1998-05-01

Conidia of Streptomyces erythreus, an industrial microbe, were implanted by nitrogen ions with energy of 40-60 keV and fluence from 1 × 10 11 to 5 × 10 14 ions/cm 2. The logarithm value of survival fraction had good linear relationship with the logarithm value of fluence. Some mutants with a high yield of erythromycin were induced by ion implantation. The yield increment was correlated with the implantation fluence. Compared with the mutation results induced by ultraviolet rays, mutation effects of ion implantation were obvious having higher increasing erythromycin potency and wider mutation spectrum. The spores of Bacillus subtilis were implanted by arsenic ions with energy of 100 keV. The distribution of implanted ions was measured by Rutherford Backscattering Spectrometry (RBS) and calculated in theory. The mechanism of mutation induced by ion implantation was discussed.

Chemical effect of Si+ ions on the implantation-induced defects in ZnO studied by a slow positron beam

NASA Astrophysics Data System (ADS)

Jiang, M.; Wang, D. D.; Chen, Z. Q.; Kimura, S.; Yamashita, Y.; Mori, A.; Uedono, A.

2013-01-01

Undoped ZnO single crystals were implanted with 300 keV Si+ ions to a dose of 6 × 1016 cm-2. A combination of X-ray diffraction (XRD), positron annihilation, Raman scattering, high resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) was used to study the microstructure evolution after implantation and subsequent annealing. A very large increase of Doppler broadening S parameters in Si+-implanted region was detected by using a slow positron beam, indicating that vacancy clusters or microvoids are induced by implantation. The S parameters increase further after annealing up to 700 °C, suggesting agglomeration of these vacancies or microvoids to larger size. Most of these defects are removed after annealing up to 1100 °C. The other measurements such as XRD, Raman scattering, and PL all indicate severe damage and even disordered structure induced by Si+ implantation. The damage and disordered lattice shows recovery after annealing above 700 °C. Amorphous regions are observed by HRTEM measurement, directly testifies that amorphous phase is induced by Si+ implantation in ZnO. Analysis of the S - W correlation and the coincidence Doppler broadening spectra gives direct evidence of SiO2 precipitates in the sample annealed at 700 °C, which strongly supports the chemical effect of Si ions on the amorphization of ZnO lattice.

Incorporation of Np(V) and U(VI) in Carbonate and Sulfate Minerals Crystallized from Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming

2015-02-15

The neptunyl Np(V)O2 + and uranyl U(VI)O2 2+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is coprecipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factorsmore » that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals.« less

Study of ion-irradiated tungsten in deuterium plasma

NASA Astrophysics Data System (ADS)

Khripunov, B. I.; Gureev, V. M.; Koidan, V. S.; Kornienko, S. N.; Latushkin, S. T.; Petrov, V. B.; Ryazanov, A. I.; Semenov, E. V.; Stolyarova, V. G.; Danelyan, L. S.; Kulikauskas, V. S.; Zatekin, V. V.; Unezhev, V. N.

2013-07-01

Experimental study aimed at investigation of neutron induced damage influence on fusion reactor plasma facing materials is reported. Displacement damage was produced in tungsten by high-energy helium and carbon ions at 3-10 MeV. The reached level of displacement damage ranged from several dpa to 600 dpa. The properties of the irradiated tungsten were studied in steady-state deuterium plasma on the LENTA linear divertor simulator. Plasma exposures were made at 250 eV of ion energy to fluence 1021-1022 ion/сm2. Erosion dynamics of the damaged layer and deuterium retention were observed. Surface microstructure modifications and important damage of the 5 μm layer shown. Deuterium retention in helium-damaged tungsten (ERD) showed its complex behavior (increase or decrease) depending on implanted helium quantity and the structure of the surface layer.

Assignment of the Stereochemistry and Anomeric Configuration of Sugars within Oligosaccharides Via Overlapping Disaccharide Ladders Using MSn

NASA Astrophysics Data System (ADS)

Konda, Chiharu; Londry, Frank A.; Bendiak, Brad; Xia, Yu

2014-08-01

A systematic approach is described that can pinpoint the stereo-structures (sugar identity, anomeric configuration, and location) of individual sugar units within linear oligosaccharides. Using a highly modified mass spectrometer, dissociation of linear oligosaccharides in the gas phase was optimized along multiple-stage tandem dissociation pathways (MSn, n = 4 or 5). The instrument was a hybrid triple quadrupole/linear ion trap mass spectrometer capable of high-efficiency bidirectional ion transfer between quadrupole arrays. Different types of collision-induced dissociation (CID), either on-resonance ion trap or beam-type CID could be utilized at any given stage of dissociation, enabling either glycosidic bond cleavages or cross-ring cleavages to be maximized when wanted. The approach first involves optimizing the isolation of disaccharide units as an ordered set of overlapping substructures via glycosidic bond cleavages during early stages of MSn, with explicit intent to minimize cross-ring cleavages. Subsequently, cross-ring cleavages were optimized for individual disaccharides to yield key diagnostic product ions ( m/ z 221). Finally, fingerprint patterns that establish stereochemistry and anomeric configuration were obtained from the diagnostic ions via CID. Model linear oligosaccharides were derivatized at the reducing end, allowing overlapping ladders of disaccharides to be isolated from MSn. High confidence stereo-structural determination was achieved by matching MSn CID of the diagnostic ions to synthetic standards via a spectral matching algorithm. Using this MSn ( n = 4 or 5) approach, the stereo-structures, anomeric configurations, and locations of three individual sugar units within two pentasaccharides were successfully determined.