In vivo NMR T2 relaxation of experimental brain tumors in the cat: a multiparameter tissue characterization.

Experimental gliomas (F98) were inoculated in cat brain for the systematic study of their in vivo T₂ relaxation time behavior. With a CPMG multi-echo imaging sequence, a train of 16 echoes was evaluated to obtain the transverse relaxation time and the magnetization M(0) at time T = 0. The magnetization decay curves were analyzed for biexponentiality. All tissues showed monoexponential T₂, only that of the ventricular fluid and part of the vital tumor tissue were biexponential. Based on these NMR relaxation parameters the tissues were characterized, their correct assignment being assured by comparison with histological slices. T₂ of normal grey and white matter was 74 ± 6 and 72 ± 6 msec, respectively. These two tissue types were distinguished through M(0) which for white matter was only 0.88 of the intensity of grey matter in full agreement with water content, determined from tissue specimens. At the time of maximal tumor growth and edema spread a tissue differentiation was possible in NMR relaxation parameter images. Separation of the three tissue groups of normal tissue, tumor and edema was based on T₂ with T_2(normal) < T_2(tumor) < T_2(edema). Using M(0) as a second parameter the differentiation was supported, in particular between white matter and tumor or edema. Animals were studied at 1–4 wk after tumor implantation to study tumor development. The magnetization M(0) of both tumor and peritumoral edema went through a maximum between the second and third week of tumor growth. T₂ of edema was maximal at the same time with 133 ± 4 msec, while the relaxation time of tumor continued to increase during the whole growth period, reaching values of 114 ± 12 msec at the fourth week. Thus, a complete characterization of pathological tissues with NMR relaxometry must include a detailed study of the developmental changes of these tissues to assure correct experimental conditions for the goal of optimal contrast between normal and pathological regions in the NMR images.     

Measurement of diffusion coefficients using a quick echo split NMR imaging technique

A new method for the ultrafast generation of diffusion-weighted images is reported. The technique combines a quick echo split NMR imaging sequence with the principle of Stejskal and Tanner. It allows to determine the diffusion constant with nearly the same accuracy as the conventional spin-echo technique, requiring only a fraction of the time. The determined values for water doped with 1 g Cu(NO₃)₂ per liter of H₂O and pure acetone were D_water = (1.95 ± 0.02) × 10⁻⁹ m²/s and D_acetone = (4.05 ± 0.02) × 10⁻⁹ m²/s at 18.5°C. They are in good agreement both with literature and our own reference measurements using a diffusion-weighted spin-echo sequence. In addition, the temperature dependence of D_water was measured in the range of 18.5–45.9°C and a good correspondence with reported data was found.     

Local structure of OH adsorbed on the Ge(0 0 1)(2 × 1) surface using scanned-energy mode photoelectron diffraction

The local geometry of OH fragments adsorbed on the Ge(0 0 1)(2 × 1) surface has been examined using O 1s scanned energy mode photoelectron diffraction. These fragments were obtained by the dissociative reaction of the clean surface with H₂O. The Ge–O bond length is found to be 1.76 ± 0.02 Å and the Ge–O bond angle to be 15° ± 2° relative to the surface normal. Some information about the positions of the Ge dimer atoms has also been obtained.     

Large solid angle X-ray photoelectron intensity distributions from CO, methoxy, and formate adsorbed on Ni(110)

Adsorbed layers of CO, methoxy (CH₃O) and formate (HCOO) on a clean Ni(110) surface are investigated by angle-resolved X-ray photoelectron spectroscopy. Large solid angle stereographic projections of C 1s or O 1s core level intensity measured for these adsorbates at 85 K show strong forward scattering enhancements that unambiguously and rather directly determine the molecular orientation, and in the case of CO, the order within the layer. CO in the (2×1) p2mg structure and methoxy are tilted by 20° and 30° relative to the normal, respectively, with the projection of the tilt in the 001 azimuth. Formate is bonded through oxygen in the bidendate configuration, aligned along the 110 azimuth. The O–C–O bond angle is determined as 124°. These results are in good agreement with previous data.     

The influence of different fabrication processes on characteristics of excess Bi2O3-doped 0.95 (Na0.5Bi0.5)TiO3–0.05 BaTiO3 ceramics

In this study, we will develop the influences of the excess x wt% (x=0, 1, 2, and 3) Bi₂O₃-doped and the different fabricating process on the sintering and dielectric characteristics of 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃ ferroelectric ceramics with the aid of SEM and X-ray diffraction patterns, and dielectric–temperature curves. The 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ ceramics are fabricated by two different processes. The first process is that (Na_0.5Bi_0.5)TiO₃ composition is calcined at 850 °C and BaTiO₃ composition is calcined at 1100 °C, then the calcined (Na_0.5Bi_0.5)TiO₃ and BaTiO₃ powders are mixed in according to 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ compositions. The second process is that the raw materials are mixed in accordance to the 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ compositions and then calcining at 900 °C. The sintering process is carried out in air for 2 h from 1120 to 1240 °C. After sintering, the effects of process parameters on the dielectric characteristics will be developed by the dielectric–temperature curves. Dielectric–temperature properties are also investigated at the temperatures of 30–350 °C and at the frequencies of 10 kHz–1 MHz.     

Effects of torsion stress on the domain wall unpinning AC field in amorphous FeCoBSi wires

The unpinning or propagation field, h_p, where domain walls are unpinned and start their displacement under the AC magnetic field of as-cast amorphous wires of nominal composition (Co₉₄Fe₆)_72.5B₁₅Si_12.5, was determined for each torsion angle between –90° (counterclockwise) and +150° (clockwise) at a constant frequency of 1 kHz. A plot of h_p as a function of torsion angle showed a sharp minimum at a torsion angle of +120. The results are interpreted in terms of the counterbalance effect of the torsion against the intrinsic helical anisotropy induced during the wire fabrication.     

Orientational alignment in solids from bidimensional isotropic-anisotropic nuclear magnetic resonance spectroscopy: applications to the analysis of aramide fibers

The use of two-dimensional isotropic-anisotropic correlation spectroscopy for the analysis of orientational alignment in solids is presented. The theoretical background and advantages of this natural-abundance ¹³C NMR method of measurement are discussed, and demonstrated with a series of powder and single-crystal variable-angle correlation spectroscopy (VACSY) experiments on model systems. The technique is subsequently employed to analyze the orientational distributions of three polymer fibers: Kevlar^® 29, Kevlar^® 49 and Kevlar^® 149. Using complementary two-dimensional NMR data recorded on synthetic samples of poly(p-phenyleneterephthalamide), the precursor of Kevlar^®, it was found that these commercial fibers possess molecules distributed over a very narrow orientational range with respect to the macroscopic director. The widths measured for these director distribution arrangements were (12 ± 1.5) ° for Kevlar^® 29, (15 ± 1.5) ° for Kevlar^® 49, and (8 ± 1.5) ° for Kevlar^® 149. These figures compare well with previous results obtained for non-commercial fiber samples derived from the same polymer.     

Ion transport studies in calcium alginate gels by magnetic resonance microscopy

Polyelectrolyte biopolymers such as calcium alginate are becoming increasingly important for the recovery of heavy metals from aqueous solutions. To understand the mechanism of ion transport in these biopolymer systems, the transport of copper ions into calcium alginate gels was investigated using proton nuclear magnetic resonance (NMR) microscopy. Copper ion transport was imaged using an inversion recovery technique which utilizes the paramagnetic effect of copper on water proton relaxation times. Diffusion experiments were performed in a diffusion cell designed to approximate a semi-infinite slab geometry at temperatures between 278 and 313 K using copper reservoir concentrations between 10 and 60 mM. The diffusion coefficient of copper in these gels was calculated from the NMR data to fit a combined diffusion-reaction model involving a diffusion term (D) and a kinetic binding term (k). At 23 °C, the diffusion coefficients in 1, 2, and 3% (w/v) gels were 3.1 · 10⁻¹⁰, 2.0 · 10⁻¹⁰, and 1.4 · 10⁻¹⁰ m²/s, respectively. The activation energy for diffusion in the 2% (w/v) gel was 28 kJ/mol.     

Solid-phase epitaxy of CaSi2 on Si(1 1 1) and the Schottky-barrier height of CaSi2/Si(1 1 1)

Thin Ca films were evaporated on Si(1 1 1) under UHV conditions and subsequently annealed in the temperature range 200–650 °C. The interdiffusion of Ca and Si was examined by ex situ Auger depth profiling. In situ monitoring of the Si 2p core-level shift by X-ray photoemission spectroscopy (XPS) was employed to study the silicide formation process. The formation temperature of CaSi₂ films on Si(1 1 1) was found to be about 350 °C. Epitaxial growth takes place at T≥400 °C. The morphology of the films, measured by atomic force microscopy (AFM), was correlated with their crystallinity as analyzed by X-ray diffraction (XRD). According to measurements of temperature-dependent I–V characteristics and internal photoemission the Schottky-barrier height of CaSi₂ on Si(1 1 1) amounts to qΦ_Bn=0.25 eV on n-type and to qΦ_Bp=0.82 eV on p-type silicon.     

Multinuclear NMR studies on the sol-gel preparation of sodium aluminophosphate glasses

Sodium aluminophosphate gels and glasses in the system NaPO₃–Al₂O₃ with P/Al ratios ranging from 9:1 to 1:1 have been synthesized by a novel sol–gel route based on the reaction of aluminum lactate with sodium polyphosphate in aqueous solution. The route from the solution to the gel and the final glass was monitored in situ by liquid and solid state NMR techniques, characterizing the influence of composition and pH on the hydrolysis, polymerization, and vitrification processes. The site distribution in the xerogels is strongly influenced by the gel-processing temperature. At temperatures near 150°C ligation with lactate groups can be nearly suppressed, resulting in maximum Al/P connectivity in the gel. Annealing the gels at temperatures near 400°C produces significant structural rearrangements, resulting in a glassy network that has close structural similarity to the glasses derived from the usual melt-cooling procedure at 1100–1450°C. This has been confirmed by extensive ²⁷Al, ³¹P and ²³Na MAS NMR as well as ²⁷Al{³¹P} and ²⁷Al {¹H} double resonance experiments. Compared to melt-cooling, the sol–gel process permits a significant extension of the glass-forming region towards higher alumina contents.     

Crystallographically-dependent ripple formation on Sn surface irradiated with focused ion beam

The metallographically polished polycrystalline Sn surface was sputtered by 30 kV focused Ga⁺ ions at room temperature. The experiment was carried out using various FIB incidence angles (0°, 15°, 30°, and 45°) over a wide range of doses (10¹⁶–10¹⁸ ions/cm²). The surface morphology was carefully characterized under the optical microscope, scanning electron microscope (SEM) and atomic force microscope (AFM). Ripples were observed on the irradiated areas even at the normal FIB incidence angle, which is not consistent with the Bradley–Harper (BH) rippling model. The orientation of ripples relies on crystallographic orientation rather than projected ion beam direction as predicted by BH model. The ripple wavelength is independent of ion dose, while ripple amplitude increases with ion dose. It is found that the ripples are formed by self-organization due to anisotropic surface diffusion in the low melting point metal.     

Studies of ionic conductivity and structural phase transitions of Na3H(SO4)2 crystal

The complex electrical impedance of Na₃H(SO₄)₂ along the b_m-axis has been measured from 25°C to 316°C in the frequency range 4 kHz–40 MHz. The temperature dependence of the electrical conductivity shows remarkable changes in the temperature range 160°C–260°C. The sample crystal becomes a fast ionic conductor above 260°C. The conduction mechanisms of proton and sodium ions in the different phases are analyzed in detail with respect to the structural features of the sample crystal.     

Measurement of the directional emittance of polycrystalline beryllium oxide

The spectral emittance of polycrystalline beryllium oxide has been measured at four different angles from 0° to 75°, at a temperature of 150°C. From the spectral measurements the average band emittance in the 8–13 μm window has been calculated. The results show that the band emittance decreases from 0.44 at the angle of 0°, down to 0.23 at an angle 75° off the normal. The low band emittance is caused by a strong reststrahlen band in the wavelength region 9.2–14 μm. This reststrahlen band has been modelled by a Lorentz one-oscillator model. Experiment and calculations show that this band of low emittance increases its width towards shorter wavelengths at inclined angles and covers almost the entire upper atmospheric window 8–13 μm at the angle of 75°.     

Structure and optical properties of sol–gel derived Gd2O3 waveguide films

Pure and rare earth doped gadolinium oxide (Gd₂O₃) waveguide films were prepared by a simple sol–gel process and dip-coating method. Gd₂O₃ was successfully synthesized by hydrolysis of gadolinium acetate. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the thermal chemistry properties of dried gel. Structure of Gd₂O₃ films annealed at different temperature ranging from 400 to 750 °C were investigated by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that Gd₂O₃ starts crystallizing at about 400 °C and the crystallite size increases with annealing temperature. Oriented growth of (4 0 0) face of Gd₂O₃ has been observed when the films were deposited on (1 0 0) Si substrate and annealed at 750 °C. The laser beam (λ=632.8 nm) was coupled into the film by a prism coupler and propagation loss of the film measured by scattering-detection method is about 2 dB/cm. Luminescence properties of europium ions doped films were measured and are discussed.     

The effects of a trace addition of silver upon elevated temperature ageing of an Al–Zn–Mg alloy

Microalloying additions of Ag (0.1 at.%) increase the hardening response of Al–Zn–Mg alloys to elevated temperature ageing in the range 100–200°C due to the formation of a high density of very fine η′ precipitate plates. The present study employed transmission electron microscopy (TEM) and three-dimension atom probe (3DAP) to study the early stages of ageing in the alloy Al–1.8Zn–3.4Mg–0.1Ag (at.%) in an attempt to identify the role of Ag in stimulating precipitation hardening. During isothermal ageing at 90°C, the hardening response is attributed to a high density of Zn–Mg–Ag rich solute clusters and GP zones. During ageing at 150°C, η′ precipitates nucleate at Zn–Mg–Ag rich solute clusters, the former growing as {111} platelets with an average composition of approximately 20 at.% Zn, 20 at.% Mg and 1.4 at.% Ag. The 3DAP data indicates that the co-segregation of Zn and Ag and subsequently Zn and Mg atoms precedes the formation of the Zn–Mg–Ag rich solute clusters. The GP zones and η′ precipitates were observed to possess a Zn:Mg ratio close to 1:1, whereas the equilibrium η precipitates possessed compositions consistent with MgZn₂. Furthermore, partitioning of Ag was observed inside all precipitate phases, viz. G.P. zones, η′ and η.     

RF-sputtered CrB2 diffusion barrier for Ni/Au Ohmic contacts on p-CuCrO2

Ohmic contacts to p-type CuCrO₂ using Ni/Au/CrB₂/Ti/Au contact metallurgy are reported. The samples were annealed in the 200–700 °C range for 60 s in flowing oxygen ambient. A minimum specific contact resistance of 2 × 10⁻⁵ Ω cm² was obtained after annealing at 400 °C. Further increase in the annealing temperature (>400 °C) resulted in the degradation of contact resistance. Auger Electron Spectroscopy (AES) depth profiling showed that out-diffusion of Ti to the surface of the contact stacks was evident by 400 °C, followed by Cr at higher temperature. The CrB₂ diffusion barrier decreases the specific contact resistance by almost two orders of magnitude relative to Ni/Au alone.     

Characterization of polyalkylvinyl ether phases by solid-state and suspended-state nuclear magnetic resonance investigations

Pure organic polyalkylvinyl ether phases were synthesized by suspension polymerization using different ratios and compositions of n-butylvinyl ether (C₄VE) and n-octadecylvinyl ether (C₁₈VE) with triethylene glycol divinyl ether or divinylbenzene as crosslinkers, respectively. These phases were investigated by means of solid-state ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (NMR) spectroscopy and ¹H high-resolution magic angle spinning (HR MAS) NMR spectroscopy in suspended-state. A comparison of these two methods showed the substantial advantages of ¹H HR MAS NMR measurements. Structure elucidation was achieved using a 2D H,H-COSY NMR experiment performed under MAS conditions enabling full peak assignment of the ¹H NMR spectra of these phases. The dynamic behavior of the polyalkylvinyl ether phases was determined by employing temperature-dependent measurements of spin–lattice relaxation times (T₁) as well as accumulation of a 2D wide line separation NMR spectrum.     

H MAS and H[Na] double resonance NMR studies on the modification of surface hydroxyl groups of γ-alumina by sodium

The modification of surface hydroxyl groups with sodium in a series of Na₂CO₃-γ-Al₂O₃ catalysts was investigated as a function of both the Na₂CO₃ loading and the calcination temperature by means of ¹H magic angle spinning (MAS) and ¹H[²³Na] spin-echo double resonance NMR techniques. The ¹H NMR experiments revealed that sodium ions are homogeneously distributed over the alumina surface and closely coordinated with the surface hydroxyl groups. In the catalysts calcined at 250 °C, the acidic hydroxyl groups (with a chemical shift of 2.0 ppm) are preferentially associated with sodium ions at low Na₂CO₃ coverages (5 and 10%), while both the acidic and the basic (0 ppm) hydroxyl groups are accessible for sodium ions at high coverages (15 and 20%). The coordination causes a low-field shift of about 2 ppm in the ¹H MAS spectra, and a broad signal at 4.5 ppm appears. It is interesting that the 4.5 ppm signal is completely suppressed in the ¹H[²³Na] MAS experiments, providing direct evidence that a strong interaction exists between adsorbed sodium ions and the surface hydroxyl groups. Increasing the calcination temperature to 450 °C results in preferential removal of the acidic hydroxyl groups, and only the most basic hydroxyl groups remain when the calcination temperature is raised to 600 °C. This is attributed to the formation of the coordinated species which enhances the acidity of the surface hydroxyl groups and prompts their dehydroxylation, especially at high calcination temperature. Correlation of the ¹H MAS NMR results and catalytic activity measurements indicates that the basic hydroxyl groups are essential for the carbonyl sulfide hydrolysis reaction.     

Fabrication of p-Si/β-FeSi2 balls/n-si structures by MBE and their electrical and optical properties

We report on the formation technique of single-crystalline β-FeSi₂ balls (<100 nm) embedded in a Si p–n junction region by Si molecular beam epitaxy (MBE). β-FeSi₂ films grown on Si (0 0 1) by reactive deposition epitaxy (RDE) aggregated into islands after annealing at 850°C in ultrahigh vacuum. The islands of β-FeSi₂ aggregated further into a ball shape by following the Si MBE overgrowth at 750°C. It was found from X-ray diffraction (XRD) patterns that the epitaxial relationship between the two materials, and single-crystalline nature were preserved even after the annealing and the Si overgrowth. Capacitance–voltage (C–V) characteristics and transmission electron microscope (TEM) images revealed that a lot of defects were introduced around the embedded β-FeSi₂ balls with an increase of embedded β-FeSi₂ quantity.     

Solution Conformation of a Pentapeptide by NMR and Molecular Modeling Studies

High resolution NMR studies and molecular modeling calculations were performed on a linear pentapeptide BOC-Tyr-Gly-Gly-Pro-Leu-OMe. This molecule exhibits two conformations in the solution state. While the ¹³C spectrum in nonpolar solvents such as acetonitrile shows only one form, in DMSO-d₆ and MeOD there are two forms. The appearance of the major (M) and minor (m) resonances is attributed to cis-trans isomerization about the X-Pro bond.

The assignments of several proton resonances for the major conformer were made through the combined analysis of two dimensional (2D) homonuclear correlated spectroscopy (COSY) and available data on similar peptides. The solution conformation of the major moiety was probed using the distance constraints obtained from 2D-NOE spectroscopy (NOESY). In addition, other information such as presence of internal hydrogen bonds and dihedral angle values from coupling constants for the amide protons were also used.