Up-regulation of Na expression in the area postrema of total sleep deprived rats by TOF-SIMS analysis

Area postrema (AP) is a circumventricular organ plays an important role in sodium homeostasis and cardiovascular regulation. Since sleep deficiency will cause cardiovascular dysfunction, the present study aims to determine whether sodium level would significantly alter in AP following total sleep deprivation (TSD). Sodium level was investigated in vivo by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Clinical manifestation of cardiovascular function was demonstrated by mean arterial pressure (MAP) values. Results indicated that in normal rats, TOF-SIMS spectrum revealed a major peak of sodium ion counting as 5.61 × 10⁵ at m/z 23. The sodium ions were homogeneous distributed in AP without specific localization. However, following TSD, the sodium intensity was relatively increased (6.73 × 10⁵) and the signal for sodium image was strongly expressed throughout AP with definite spatial distribution. MAP of TSD rats is 138 ± 5 mmHg, which is significantly higher than that of normal ones (121 ± 3 mmHg). Regarding AP is an important area for sodium sensation and development of hypernatremic related sympatho-excitation; up-regulation of sodium expression following TSD suggests that high sodium level might over-activate AP, through complex neuronal networks involving in sympathetic regulation, which could lead to the formation of TSD relevant cardiovascular diseases.     

Nano-crater formation on a Si(1 1 1)-(7 × 7) surface by slow highly charged ion-impact

Using scanning tunneling microscopy (STM) and time of flight secondary ion mass spectrometry (TOF/SIMS), we observed radiation effects on a Si(1 1 1)-(7 × 7) surface in the collision of a single highly charged ion (HCI) with a charge state q up to q = 50. The STM observation with atomic resolution revealed that a nanometer sized crater-like structure was created by a single HCI impact, where the size increased rapidly with q. The secondary ion yields also increased with q in which multiply charged Si ions (Siⁿ⁺) were clearly observed in higher q HCI-collisions. The sputtering mechanism is briefly discussed, based on the so-called Coulomb explosion model.     

Analysis of intensities of positive and negative ion species from silicon dioxide films using time-of-flight secondary ion mass spectrometry and electronegativity of fragments

Intensities of positive and negative ion species emitted from thermally oxidized and plasma-enhanced chemical vapor deposited (PECVD) SiO₂ films were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and the Saha-Boltzmann equation. Intensities of positive and negative secondary ion species were normalized to those of ²⁸Si⁺ and ²⁸Si⁻ ions, respectively, and an effective temperature of approximately (7.2 ± 0.1) × 10³ K of the sputtered region bombarded with pulsed 22 kV Au₃⁺ primary ions was determined. Intensity spectra showed polarity dependence on both n and m values of Si_nO_m fragments, and a slight shift to negative polarity for PECVD SiO₂ compared to thermally oxidized SiO₂ films. By dividing the intensity ratios of negative-to-positive ions for PECVD SiO₂ by those for thermally oxidized SiO₂ films to cancel statistical factors, the difference in absolute electronegativity (half the sum of ionization potential and electron affinity of fragments) between both films was obtained. An increase in electronegativity for SiO_m (m = 1, 2) and Si₂O_m (m = 1-4) fragments for PECVD SiO₂ films compared to thermally oxidized films was obtained to be 0.1-0.2 Pauling units, indicating a more covalent nature of Si-O bonds for PECVD SiO₂ films compared to the thermally oxidized SiO₂ films.     

Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au_xH_yS_z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au_xH_yS_z (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au_xH_yS_z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na⁺, (M+H)Na⁺, AuMNa⁺, (M₂−S)Na⁺, and M₂Na⁺ are determined, and also in cationized forms with K⁺. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM₂ and Au₂M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au_xM_w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.     

Influence of primary ion species on the secondary cluster ion emission process from SAMs of hexadecanethiol on gold

In order to investigate the secondary cluster ion emission process of organo-metallic compounds under keV ion bombardment, self-assembled monolayers (SAMs) of alkanethiols on gold are ideal model systems. In this experimental study, we focussed on the influence of the primary ion species on the emission processes of gold-alkanethiolate cluster ions from a hexadecanethiol SAM on gold. For this purpose, we carried out time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements using the following primary ion species and acceleration voltages: Ar⁺, Xe⁺, SF₅⁺ (10 kV), Bi⁺, Bi₃⁺(25 kV), Bi₃²⁺, Bi₅²⁺, Bi₇²⁺ (25 kV).It is well known that molecular ions M⁻ and gold-alkanethiolate cluster ions Au_xM_y⁻ with M = S-(CH₂)₁₅-CH₃, x − 3 ≤ y ≤ x + 1, x, y > 0, show intense peaks in negative mass spectra. We derived yields Y_SI exemplarily for the molecular ions M⁻ and the gold-hexadecanethiolate cluster ions Au_y+1M_y⁻ up to y = 8 and found an exponentially decreasing behaviour for increasing y-values for the cluster ions.In contrast to the well-known increase in secondary ion yield for molecular secondary ions when moving from lighter to heavier (e.g. Ar⁺ to Xe⁺) or from monoatomic to polyatomic (e.g. Xe⁺ to SF₅⁺) primary ions, we find a distinctly different behaviour for the secondary cluster ions. For polyatomic primary ions, there is a decrease in secondary ion yield for the gold-hexadecanethiolate clusters whereas the relative decrease of the secondary ion yield ξ_Y with increasing y remains almost constant for all investigated primary ions.     

The influence of the cholesterol microenvironment in tissue sections on molecular ionization efficiencies and distributions in ToF-SIMS

High-resolution images of cholesterol were obtained from Lymnaea stagnalis nervous tissue using metal-assisted (MetA) time-of-flight secondary ion mass spectrometry (ToF-SIMS). The spatial distributions of different pseudomolecular ions of cholesterol [M − H]⁺, [M − OH]⁺ and [2M + Au]⁺, illustrate the influence of the tissue microenvironment on the ionization efficiencies of these ions. These biological matrix effects result in differences in localizations of molecular ions derived from the same molecular species.     

High-intensity Si cluster ion emission from a silicon target bombarded with large Ar cluster ions

Secondary ions emitted from Si targets were measured with a quadrupole mass spectrometer under large Ar cluster and monomer ion bombardment. Incident ion beams with energies from 7.5 to 25 keV were used and the mean size of the Ar cluster ion was about 1000 atoms/cluster. Si_n⁺ ions with n values up to n = 8 were detected under Ar cluster ion bombardment, whereas Si cluster ions were scarcely detected under Ar monomer ion bombardment. These cluster ion yields showed the power law dependence on the cluster size.     

Low temperature sintering of sub-stoichiometric Ni-Cu-Zn ferrites: Shrinkage, microstructure and permeability

We have studied sub-stoichiometric Ni-Cu-Zn ferrites with iron deficiency (i.e., <50mol% Fe₂O₃) of composition Ni_0.20Cu_0.20Zn_0.60+zFe_2−zO_4−(z/2) with 0≤z≤0.06. The temperature of maximum shrinkage rate is shifted from T=1000 °C for z=0 towards lower temperatures down to T=900 °C for a sub-stoichiometric ferrite with z=0.02. Dense samples are obtained after firing at 900 °C for z>0 only. Sub-stoichiometric compositions (z>0) do not form single-phase spinel ferrites after sintering at 900 °C, but rather represent mixtures of CuO and a stoichiometric ferrite with slightly modified composition. The formation of small amounts of CuO at grain boundaries is demonstrated by XRD and SEM. The permeability is increased from μ=80 for stoichiometric ferrites (z=0) to μ=660 for z=0.02. The formation of CuO during sintering of sub-stoichiometric ferrites supports densification and is a prerequisite for low temperature firing of multilayer inductors. Addition of 1 wt% Bi₂O₃ as liquid phase sintering aid is required to provide sufficient densification of the stoichiometric ferrite (z=0) at 900 °C. Addition of 0.37 wt% Bi₂O₃ to a sub-stoichiometric ferrite (z=0.02) results in dense samples after firing at 900 °C; however, the microstructure formation is dominated by heterogeneous grain growth.     

Analysis of TOF-SIMS spectra from fullerene compounds

We analyzed TOF-SIMS spectra obtained from three different size of fullerenes (C₆₀, C₇₀ and C₈₄) by using Ga⁺, Au⁺ and Au₃⁺ primary ion beams and investigated the fragmentation patterns, the enhancement of secondary ion yields and the restraint of fragmentation by using cluster primary ion beams compared with monoatomic primary ion beams. In the TOS-SIMS spectra from C₇₀ and C₈₄, it was found that a fragment ion, identified as C₆₀⁺ (m/z = 720), showed a relatively high intensity compared with that of other fragment ions related to C₂ depletion. It was also found that the Au₃⁺ bombardment caused intensity enhancement of intact molecules (C₆₀⁺, C₇₀⁺ and C₈₄⁺) and restrained the fragmentation due to C₂ depletion.     

The peculiarities of the low-energy ion scattering by polycrystal targets

In the present work, experimental and computer simulation studies of low-energy (E₀ = 80-500 eV) Cs⁺ ions scattering on Ta, W, Re target surfaces and K⁺ ions scattering on Ti, V, Cr target surfaces have been performed for more accurate definition of mechanism of scattering, with a purpose of evaluation of an opportunity of use of slow ions scattering as a tool of surface layers analysis. The choice of the targets was based on the fact that the ratios of atomic masses of target atoms and ions μ = m₂/m₁ were almost the same for all cases considered and greater than 1 (direct mass ratio) however, the difference of binding energies of target atoms in the cases of Cs⁺ and K⁺ scattering was almost twice as much. It has been noticed that the dependencies of the relative energy retained by scattering ions at the maximum of energy distribution versus the initial energy E_m/E₀ (E₀) have a similar shape in all cases. The relative energy retained by scattering ions increases while the initial energy of incidence ions decreases. The curves are placed above each other relative to the binding energies of target atoms, to show what this says about the influence of binding energy on a process of scattering of low-energy ions. The correlation between value of energy change maintained by an ion for different values of E₀ in the case of scattering by targets with different masses of atoms and its binding energies is experimentally established. The contrary behavior of the E_m/E₀ (E₀) dependencies concerning the target atom binding energy quantity E_b for cases with direct (μ > 1) and inverse (μ < 1) mass ratio of colliding particles is established. The comparison of experimental energy distributions with calculated histograms shows that the binary collision approximation cannot elucidate the abnormally great shift in the maxima of relative energy distributions towards greater energy retained by scattering ions.     

Formation of Sim and SimCn clusters by C60 sputtering of Si

The secondary ion mass spectrum of silicon sputtered by high energy C₆₀⁺ ions in sputter equilibrium is found to be dominated by Si clusters and we report the relative yields of Si_m⁺ (1 ≤ m ≤ 15) and various Si_mC_n⁺ clusters (1 ≤ m ≤ 11 for n = 1; 1 ≤ m ≤ 6 for n = 2; 1 ≤ m ≤ 4 for n = 3). The yields of Si_m⁺ clusters up to Si₇⁺ are significant (between 0.1 and 0.6 of the Si⁺ yield) with even numbered clusters Si₄⁺ and Si₆⁺ having the highest probability of formation. The abundances of cluster ions between Si₈⁺ and Si₁₁⁺ are still significant (>1% relative to Si⁺) but drop by a factor of ∼100 between Si₁₁⁺ and Si₁₃⁺. The probability of formation of clusters Si₁₃⁺-Si₁₅⁺ is approximately constant at ∼5 × 10⁻⁴ relative to Si⁺ and rising a little for Si₁₅⁺, but clusters beyond Si₁₅ are not detected (Si_m≥16⁺/Si⁺ < 1 × 10⁻⁴). The probability of formation of Si_m⁺ and Si_mC_n⁺ clusters depends only very weakly on the C₆₀⁺ primary ion energy between 13.5 keV and 37.5 keV. The behaviour of Si_m⁺ and Si_mC_n⁺ cluster ions was also investigated for impacts onto a fresh Si surface to study the effects that saturation of the surface with C₆₀⁺ in reaching sputter equilibrium may have had on the measured abundances. By comparison, there are very minor amounts of pure Si_m⁺ clusters produced during C₆₀⁺ sputtering of silica (SiO₂) and various silicate minerals. The abundances for clusters heavier than Si₂⁺ are very small compared to the case where Si is the target.The data reported here suggest that Si_m⁺ and Si_mC_n⁺ cluster abundances may be consistent in a qualitative way with theoretical modelling by others which predicts each carbon atom to bind with 3-4 Si atoms in the sample. This experimental data may now be used to improve theoretical modelling.     

Molecular imaging of in vivo calcium ion expression in area postrema of total sleep deprived rats: Implications for cardiovascular regulation by TOF-SIMS analysis

Excessive calcium influx in chemosensitive neurons of area postrema (AP) is detrimental for sympathetic activation and participates in the disruption of cardiovascular activities. Since total sleep deprivation (TSD) is a stressful condition known to harm the cardiovascular function, the present study is aimed to determine whether the in vivo calcium expression in AP would significantly alter following TSD by the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) and calretinin (a specific calcium sensor protein in AP neurons) immunohistochemistry. The results indicated that in normal rats, the calcium intensity was estimated to be 0.5 × 10⁵ at m/z 40.08. However, following TSD, the intensity for calcium ions was greatly increased to 1.2 × 10⁵. Molecular imaging revealed that after TSD, various strongly expressed calcium signals were distributed throughout AP with clear identified profiles instead of randomly scattered within this region in normal rats. Immunohistochemical staining corresponded well with ionic image in which a majority of calcium-enriched gathering co-localized with calretinin positive neurons. The functional significance of TSD-induced calcium augmentation was demonstrated by increased heart rate and mean arterial pressure, clinical markers for cardiovascular dysfunction. Considering AP-mediated sympathetic activation is important for cardiovascular regulation, exaggerated calcium influx in AP would render this neurocircuitry more vulnerable to over-excitation, which might serve as the underlying mechanism for the development of TSD-relevant cardiovascular deficiency.     

Exploration of layered-type pseudo four-component Li-Ni-Co-Ti oxides

A series of layered-type pseudo four-component Li-Ni-Co-Ti oxides were prepared to explore optimal cathode materials for a lithium-ion secondary battery. The new layered-type compounds were prepared using a combinatorial material-preparation system based on electrostatic spray deposition (the “M-ist Combi” system), and combinatorial powder X-ray diffraction. The composition region of the new compounds (Li_α(Ni_xCo_yTi_z)O₂ (α∼1, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, z∼0.2, x + y + z = 1.0)) was found to be wider than the composition region previously reported (LiNi_0.8−yCo_0.2Ti_yO₂ (0 ≤ y ≤ 0.1)).     

Surface morphology of metal films deposited on mica at various temperatures observed by atomic force microscopy

Thin films of eight metals with a thickness of 150 nm were deposited on mica substrates by thermal evaporation at various temperatures in a high vacuum. The surface morphology of the metal films was observed by atomic force microscopy (AFM) and the images were characterized quantitatively by a roughness analysis and a bearing analysis (surface height analysis). The films of Au, Ag, Cu, and Al with the high melting points were prepared at homologous temperatures T/T_m = 0.22-0.32, 0.40, and 0.56. The films of In, Sn, Bi, and Pb with the low melting points were prepared at T/T_m = 0.55-0.70, where T and T_m are the absolute temperatures of the mica substrate and the melting point of the metal, respectively. The surface morphology of these metal films was studied based on a structure zone model. The film surfaces of Au, Ag, and Cu prepared at the low temperatures (T/T_m = 0.22-0.24) consist of small round grains with diameters of 30-60 nm and heights of 2-7 nm. The surface heights of these metal films distribute randomly around the surface height at 0 nm and the morphology is caused by self-shadowing during the deposition. The grain size becomes large due to surface diffusion of adatoms and the film surfaces have individual characteristic morphology and roughnesses as T increases. The surface of the Al film becomes very smooth as T increases and the atomically smooth surface is obtained at T/T_m = 0.56-0.67 (250-350 °C). On the other hand, the atomically smooth surface of the Au film is obtained at T/T_m = 0.56 (473 ± 3 °C). The films of In, Sn, Bi, and Pb prepared at T/T_m = 0.55-0.70 also show the individual characteristic surface morphology.     

Variable temperature EPR spectra of Copper (II) ions in kainite crystals

X-band electron paramagnetic resonance (EPR) studies on divalent copper ions embedded in KMgClSO₄·3H₂O single crystals have been performed at low temperature (123 K). The angular variation of the EPR spectra reveals the presence of two Cu²⁺ sites, which have different orientations. The spin-Hamiltonian parameters of this six-coordinated cupric ion have been evaluated from the EPR spectra at 123 K. The forbidden lines due to Δm_I=±1 transitions are observed in between allowed transitions. The temperature variation EPR studies have also been performed both for a single crystal and a polycrystalline sample. The ground state wavefunction of Cu²⁺ ions has been estimated and is found to be an admixture of d_3z²−r² and d_x²−y². The temperature variation of the EPR spectra reveals that Cu²⁺ ions exhibit dynamic Jahn-Teller effect. From the polycrystalline EPR data, the temperature dependent magnetic susceptibilities are evaluated and discussed.     

Formation of GaAs1−xNx nanofilm on GaAs by low energy N2 implantation

Nitridation of GaAs (1 0 0) by N₂⁺ ions with energy E_i = 2500 eV has been studied by Auger- and Electron Energy Loss Spectroscopy under experimental conditions, when electrons ejected only by nitrated layer, without contribution of GaAs substrate, were collected. Diagnostics for quantitative chemical analysis of the nitrated layers has been developed using the values of NKVV Auger energies in GaN and GaAsN chemical phases measured in one experiment, with the accuracy being sufficient for separating their contributions into the experimental spectrum. The conducted analysis has shown that nanofilm with the thickness of about 4 nm was fabricated, consisting mainly of dilute alloy GaAs_1−xN_x with high concentration of nitrogen x ∼ 0.09, although the major part of the implanted nitrogen atoms are contained in GaN inclusions. It was assumed that secondary ion cascades generated by implanted ions play an important role in forming nitrogen-rich alloy.     

Enhancement effect in photon-stimulated ion desorption for benzene adsorbed on silicon surfaces observed using angle-dependent technique

We have investigated photon-stimulated ion desorption from deuterated benzene (C₆D₆) adsorbed on Si(1 0 0) and Si(1 1 1) surfaces following C 1s core excitation. Using time-of-flight mass spectrometry combined with angle-dependent technique, we measured the dependences of mass-spectra of desorption ions on photon energies and on incident angle (θ) of synchrotron beam. We have found the ion yields for adsorbate-derived fragments of CD⁺ and CD₂⁺ are enhanced in very small angles of incident X-rays. Moreover, molecular orientation effect appeared in excitation energy dependences of D⁺ ions from the Si(1 0 0) and Si(1 1 1) surfaces; that is, ion yield spectra measured at θ = 10° are different from that at θ = 65°. Furthermore, it was found that desorption ion yields increase greatly with decreasing incident angles. The angular dependences are consistently similar for all ion species, excitation energies, and indexes of substrates. Possible desorption processes are described on the basis of the observations.     

Effects of thermal light source properties in two-photon subwavelength coincidence interference experiments

We perform two-photon coincidence subwavelength interference experiments from double slit using independent photons obtained from a pseudo-thermal light source produced by (i) slowly rotating ground glass (RGG) with turbid solution of a different density and (ii) RGG. The turbid solution is water solution containing 3 μm diameter polystyrene microspheres. It is found that the visibility of the obtained interference pattern decreases in first experiment with increasing the density of the turbid solution from N = 10¹⁰ spheres m⁻³ to N = 10¹⁴ spheres m⁻³. However, the results are reported here for the density of N = 10¹⁴ spheres m⁻³. The visibility obtained with RGG with turbid solution having N = 10¹⁴ spheres m⁻³is 23% which increases to 27% with RGG but the resolution decreases. The effect of coherence width of source in two-photon interference pattern is also studied with pseudo-thermal light obtained by RGG. It was observed that on increasing the coherence width the visibility of interference fringes increased and quality of the fringe reduced and when the coherence width was more then slit separation, in coincidence measurements, no interference pattern appeared. The results are used to explore the classical subwavelength interference nature with thermal light.     

Magnetic hyperfine fields for Sn atoms in rare-earth intermetallides: huge deviation from proportionality between Bhf and Sz

The magnetic hyperfine fields for ¹¹⁹Sn impurity atoms, localized in Ga sites of ferromagnetic intermetallic compounds RGa (R=Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, and Tm), were measured by the Mössbauer spectroscopy technique. At T=5 K, the hyperfine field value (B_hf) varies from 3.3 T in TmGa to 28.0 T in GdGa. Huge deviation from the proportionality between B_hf and the projection of the R³⁺ ion spin (S_z=(g−1)J) was found. As the atomic number of the R element increases, the B_hf/S_z ratio drastically decreases from 12.6 T for PrGa to 3.3 T for TmGa. This unexpected result can be explained by the strong dependency of B_hf value on the relationship between the Sn-R atomic separation (R_nn) and the radius of the magnetic 4f shell (R_4f). In the framework of this concept, the available experimental data for Sn atom in the rare-earth compounds with non-magnetic sp elements were considered. The data may be described by the universal dependency on the single parameter, λ=R_nn/R_4f.     

Tunable distributed feedback lasing with low threshold and high slope efficiency from electroluminescent conjugated polymer waveguide

We present here tunable lasing from holographic distributed feedback (DFB) resonator of electroluminescent conjugated polymer waveguide. Tunable holographic lasing from 560 to 590 nm was simply achieved by rotating a Lloyd-mirror waveguide configuration. Lasing performance for the first order (m = 1) is superior to that for the second order (m = 2). Threshold for lasing for m = 1 is in the range of 25 to 50 μJ/cm²/pulse, which is close to that for amplified spontaneous emission (ASE), and that for m = 2 is larger than 104 μJ/cm²/pulse. For m = 1, slope efficiency of 7.3% including ASE in addition to lasing emission was measured, whereas for m = 2 slope efficiency between 0.1 and 0.2% was measured.