27Al pulsed nuclear magnetic resonance study of CeAl2

The magnetic properties and the electronic structures of a rare-earth aluminum intermetallic compound CeAl₂ are investigated by magnetic susceptibility measurements and ²⁷Al pulsed nuclear magnetic resonance (NMR) techniques. The magnetic susceptibility is strongly temperature-dependent, following a Curie–Weiss law down to ∼12 K, and shows an antiferromagnetic transition at 4 K. The ²⁷Al NMR spectra show a typical powder pattern for a nuclear spin I of 5/2 with the second-order nuclear quadrupole interaction at high temperature and an additional large dipolar broadening between the 4f electron spins of cerium and the ²⁷Al nuclear spins at low temperature. The ²⁷Al NMR Knight shift follows the same temperature dependence as the magnetic susceptibility, suggesting that the ²⁷Al NMR Knight shift originates from the transferred hyperfine field of the Ce 4f electron spins with the hyperfine coupling constant of A = +5.7 kOe/μ_B. The spin-lattice relaxation rate 1/T₁ is roughly proportional to temperature, as with most non-magnetic metals at high temperature, and then strongly temperature-dependent, increasing rapidly with a peak near the antiferromagnetic transition temperature and decreasing at lower temperature. The temperature dependence of the Korringa ratio K, however, suggests that the antiferromagnetic spin fluctuation signature, which is an enhancement in the Korringa ratio, is washed out owing to the geometrical cancellation of Ce 4f fluctuations at the Al sites.     

Total strength of the magnetic dipole resonance in <Superscript>27</Superscript>Al

The γ decay of the resonance-like structure observed in the ²⁶Mg(pγ)²⁷ Al reaction in the energy range E _p = 0.8–3.0 MeV of accelerated protons has been investigated. The M1 resonance on the ground and excited states of ²⁷Al with E* = 844 and 1014 keV is identified. The total strength of the M1 resonance on the ground state of this nucleus is determined. The position and total strength of this resonance are explained taking into account pairing forces.     

A combined 14N/27Al nuclear magnetic resonance and powder X-ray diffraction study of impurity phases in beta-sialon ceramics

Beta-sialons are ceramic phases occurring in the SiO(2)-Si(3)N(4)-AlN-Al(2)O(3) system. A series of samples with differing compositions has been investigated by magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy and powder X-ray diffraction (XRD). Although the constituent nitrogen nuclei occupy positions of low symmetry in the beta-sialon structure, 14N NMR spectra could be recorded for the samples examined. The origin of the 14N signal could be traced to the presence of an aluminium nitride (AlN) impurity phase with the help of 27Al NMR and XRD results. Similarly, the existence of Al(2)O(3) grains could be readily detected for a number of samples. Thus, the combination of 14N and 27Al NMR is shown to be an especially effective tool in identifying and characterizing impurity phases in sialon ceramics, complementing the results obtained from standard XRD analysis.     

A crossover from the magnetic Kondo compound CeCu5 to the heavy Fermion compounds CeCu4Al and CeCu3Al2

We present measurements on the isostructural series CeCu₅, CeCu₄Al and CeCu₃Al₂, which demonstrate the supression of the antiferromagnetic phase transition at 4 K in CeCu₅, due to the substitution of Cu by Al in CeCu₄Al and CeCu₃Al₂. This substitution, however, is linked to a dramatic enhancement of properties reflecting the electronic density of states.     

A multinuclear magnetic resonance study of intramolecular hydrogen bonding in some Schiff and Schiff-Mannich bases in solution and in the solid state

Two Schiff bases; N, N′-bis(5-bromosalicylidene)-1,2-diaminoethane, BS, and 7-[(1-{5-bromo-2-hydroxyphenyl} methylidene)amino]-4-methylcoumarin, Sc, and two appropriate Schiff–Mannich bases, N, N′-bis{5-bromo-3-[(diethylamino)methyl]salicylidene}-1,2-diaminoethane, BSM, and 7-[(1-{5-bromo-3-[(diethylamino)methyl]-2-hydroxyphenyl} methylidene)amino]-4-methylcoumarin, SMc, capable of intramolecular hydrogen bonding have been investigated by multinuclear magnetic resonance methods in both solid and liquid phases. In all of the compounds under investigation tautomeric equilibrium involving an intramolecular hydrogen bond has been found. The Schiff–Mannich bases, which can form two different kinds of H bonds at room temperature, form relatively weak H bonds with the imino nitrogen atoms. At low temperatures the tautomeric proton exchange becomes slow on the NMR time scale and both hydrogen-bonded forms can be observed by ¹H, ¹³C, and ¹⁵N NMR methods. In the solid state the tautomeric process is frozen and only one H-bonded form is present. On the basis of 13C and ¹⁵N CPMAS NMR spectra this is identified as the form with hydrogen bonds involving the imino groups. This conclusion is in good agreement with previous results obtained by X-ray diffraction methods.

The investigated Schiff bases (BS and Sc) form relatively weak H bonds. The proton position in the hydrogen bridge, estimated from ¹⁵N and ¹³C chemical shifts, is very similar in both the solution and solid phases. In chloroform solution the observed tautomeric equilibria are almost insensitive to a temperature change within the range 223 to 303 K.     

Structural characterisation of the silica and alumina Zener pinning phases in nanocrystalline CeO2 by 29Si and 27Al nuclear magnetic resonance

Nanocrystalline CeO₂ samples have been manufactured using sol-gel techniques, containing either 15 % silica or 10 % alumina by weight to restrict growth of the ceria nanocrystals during annealing by Zener pinning. ²⁹Si and ²⁷Al MAS NMR have been used to investigate the structure of these pinning phases over a range of annealing temperatures up to 1000 °C, and their effect on the CeO₂ morphology has been studied using electron microscopy. The silica pinning phase resulted in CeO₂ nanocrystals of average diameter 19 nm after annealing at 1000 °C, whereas the alumina pinned nanocrystals grew to 88 nm at the same temperature. The silica pinning phase was found to contain a significant amount of inherent disorder indicated by the presence of lower n Qⁿ species even after annealing at 1000 °C. The alumina phase was less successful at restricting the growth of the ceria nanocrystals, and tended to separate into larger agglomerations of amorphous alumina, which crystallised to a transition alumina phase at higher temperatures.     

Recoil properties of27Mg from the27Al(γ, π+)27Mg reaction

The mean ranges of the recoil nuclei from the reaction²⁷Al(γ, π⁺)²⁷Mg have been measured at maximum bremsstrahlung energies of 250, 400 and 800 MeV using catcher-foil techniques. The experimentally-determined ranges in directions along and perpendicular to the photon beam are in good agreement with calculated values based on the Fermi gas model and the impulse approximation.     

Nuclear magnetic resonance of 27Al in the lutetium aluminum garnet

By NMR, the quadrupole coupling constants of ²⁷Al for the a- and d-sites in Lu₃Al₂ (AlO₄)₃ have been determined at 300 and 4.2 K. Structural consequences are discussed and compared with other rare earth aluminum garnets.     

Novel mineral contrast agent for magnetic resonance studies of bone implants grown on a chick chorioallantoic membrane

Magnetic resonance imaging (MRI) studies of tissue engineered constructs prior to implantation clearly demonstrate the utility of the MRI technique for studying the bone formation process. To test the utility of our MRI protocols for explant studies, we present a novel test platform in which osteoblast-seeded scaffolds were implanted on the chorioallantoic membrane of a chick embryo. Scaffolds from the following experimental groups were examined by high-resolution MRI: (a) cell-seeded implanted scaffolds (CIM), (b) unseeded implanted scaffolds (UCIM), (c) cell-seeded scaffolds in static culture (CIV) and (d) unseeded scaffolds in static culture (UCIV). The reduction in water proton transverse relaxation times and the concomitant increase in water proton magnetization transfer ratios for CIM and CIV scaffolds, compared to UCIV scaffolds, were consistent with the formation of a bone-like tissue within the polymer scaffold, which was confirmed by immunohistochemistry and fluorescence microscopy. However, the presence of angiogenic vessels and fibrotic adhesions around UCIM scaffolds can confound MRI findings of bone deposition. Consequently, to improve the specificity of the MRI technique for detecting mineralized deposits within explanted tissue engineered bone constructs, we introduce a novel contrast agent that uses alendronate to target a Food and Drug Administration-approved MRI contrast agent (Gd-DOTA) to bone mineral. Our contrast agent termed GdALN was used to uniquely identify mineralized deposits in representative samples from our four experimental groups. After GdALN treatment, both CIM and CIV scaffolds, containing mineralized deposits, showed marked signal enhancement on longitudinal relaxation time-weighted (T1W) images compared to UCIV scaffolds. Relative to UCIV scaffolds, some enhancement was observed in T1W images of GdALN-treated UCIM scaffolds, subjacent to the dark adhesions at the scaffold surface, possibly from dystrophic mineral formed in the fibrotic adhesions. Notably, residual dark areas on T1W images of CIM and UCIM scaffolds were attributable to blood inside infiltrating vessels. In summary, we present the efficacy of GdALN for sensitizing the MRI technique to the deposition of mineralized deposits in explanted polymeric scaffolds.     

High resolution gamma-ray spectroscopy of the27Al(p,γ)28Si resonance reaction

High resolution gamma-ray spectra have been measured from the²⁷Al (p,γ)²⁸Si reaction for the resonances atE _p=2·482, 2·511 and 2·735 MeV at ϑ _pγ=0°, 30°, 55° and 90° using a Ge (Li) gamma spectrometer. From the spectra and the angular distributions the properties of the resonance states have been obtained. These states are the isobaric analogues of the levels at 4·69, 4·75 and 4·93MeV levels respectively in the parent nucleus A²⁸l.     

Imaging of electrically detected magnetic resonance of a silicon wafer.

An imaging technique of electrically detected magnetic resonance (EDMR) was newly developed. Because the EDMR signal is obtained from paramagnetic recombination centers, one may expect the image to represent the distribution of defect and/or impurity sites in the sample. We successfully obtained EDMR images of a light-illuminated silicon plate 8 mm in width and 15 mm in length, which was cut from a silicon wafer (n-type, 100 Omega cm), under ESR irradiation at a frequency of 890 MHz (wavelength, 340 mm). The reproducibility of the EDMR image obtained from a sample was amply satisfactory. When the oxidized surface of the silicon was removed, the EDMR signal disappeared. Although the EDMR signal reappeared when the surface of the sample became reoxidized, the EDMR image obtained was slightly different from the earlier one. This finding shows that the EDMR image obtained from the sample shows the distribution of defects at the Si/SiO(2) interface.     

3D reconstruction of the brain from magnetic resonance images using a connectivity algorithm

We present high resolution three dimensional (3D) connectivity, surface construction and display algorithms that detect, extract, and display the surface of a brain from contiguous magnetic resonance (MR) images. The algorithms identify the external brain surface and create a 3D image, showing the fissures and surface convolutions of the cerebral hemispheres, cerebellum, and brain stem. Images produced by these algorithms also show the morphology of other soft tissue boundaries such as the cerebral ventricular system and the skin of the patient. For the purposes of 3D reconstruction, our experiments show that T1 weighted images give better contrast between the surface of the brain and the cerebral spinal fluid than T2 weighted images. 3D reconstruction of MR data provides a non-invasive procedure for examination of the brain surface and other anatomical features.     

The assignment of molecular infrared spectra from a laser magnetic resonance spectrometer

Mathematical techniques are presented which have proved useful in assigning the laser magnetic resonance pure-rotation spectrum of HO₂, i.e., useful in assigning an absorption spectrum obtained when molecular energy levels are Zeeman shifted by an external magnetic field until transition frequencies coincide with a fixed-frequency radiation source. The techniques described should have general applicability to the laser magnetic resonance vibration-rotation spectrum of any molecule in an orbitally nondegenerate electronic state and a doublet electronic spin state ($\text{S =}\text{1}\text{2}$). Equations involving both Zeeman line positions and Zeeman line intensities are presented. These allow the assignment of M_J quantum numbers, the determination of the spin-rotation interaction constant γ and rotational quantum number N for both the upper and the lower state, and the determination of the zero-field transition frequency. The equations can be used without prior knowledge of the molecular structure or energy levels.     

Field dependence of the ground state in the exotic superconductor CeCoIn5: a nuclear magnetic resonance investigation

We report 115In nuclear magnetic resonance (NMR) measurements in CeCoIn5 at low temperature (T approximately 70 mK) as a function of the magnetic field (H0) from 2 to 13.5 T applied perpendicular to the c axis. A NMR line shift reveals that below 10 T the spin susceptibility increases as sqrt[H0]. We associate this with an increase of the density of states due to the Zeeman and Doppler-shifted quasiparticles extended outside the vortex cores in a d-wave superconductor. Above 10 T a new superconducting state is stabilized, possibly the modulated phase predicted by Fulde, Ferrell, Larkin, and Ovchinnikov. This phase is clearly identified by a strong and linear increase of the NMR shift with the field, before a jump at the first order transition to the normal state.