NMR: hyperfine interactions in oxides and metals

A NMR characterisation is given of various polymorphs of TiO₂ (anatase, rutile and brookite), Ti₂O₃, perovskites CaTiO₃ and BaTiO₃, FeTiO₃, TiB₂, titanium metal, the titanium aluminides Ti₃Al, TiAl, TiAl₂, TiAl₃, and TiAg. Values of chemical or Knight shift, nuclear quadrupole coupling constant and asymmetry parameter were derived from the (1/2, −1/2) powder lineshapes. For TiB₂, titanium metal, TiAl, and TiAl₃, where ±(1/2, 3/2), and higher satellite transitions were observed, a value for the axial component of the Knight shift was obtained.     

Mg NMR site analysis in metals and intermetallics

Nuclear magnetic resonance (NMR) of the low abundance and low gyromagnetic ratio isotope ²⁵Mg, I=5/2, 2.606 MHz/T, 10% abundant, is shown here to provide an informative probe for phase identification, site symmetry and site multiplicity of the intermetallic compounds which occur as strengthening precipitate phases in lightweight alloys. The intermetallics discussed here, Mg₁₇Al₁₂, MgZn₂, Mg₂Al₃ and Al₂CuMg, are the final equilibrium precipitate phases in a number of Mg- and Al-based heat-treatable alloys. The ²⁵Mg spectra of Mg in Al–10 at%Mg alloy show the progressive precipitation of Mg₂Al₃ from Mg in solid solution as a function of annealing time at 150 °C. Also reported are ²⁵Mg spectra for CuMg₂, Mg₄₄Al₁₅Zn₄₁ and Mg₂Sn, along with the counter atom ⁶⁷Zn and ⁶³Cu NMR spectra for MgZn₂ and CuMg₂. All spectra are simulated to determine nuclear interaction parameters and confirm site occupancy.     

Sequentially acquired two-dimensional NMR spectra from hyperpolarized sample

A scheme capable of acquiring heteronuclear 2D NMR spectra of hyperpolarized sample is described. Hyperpolarization, the preparation of nuclear spins in a polarized state far from thermal equilibrium, can increase the NMR signal by several orders of magnitude. It presents opportunities to apply NMR spectroscopy to dilute samples that would otherwise yield insufficient signal. However, conventional 2D NMR spectroscopy, which is commonly applied for the determination of molecular structure, relies on the recovery of the initial polarization after each transient. For this reason, it cannot be applied directly to a sample that has been hyperpolarized once. With appropriately modified pulse schemes, two-dimensional NMR spectra an however be acquired sequentially by utilizing a small portion of the hyperpolarized signal in every scan, while keeping the remaining polarization for future scans. We present heteronuclear multi-quantum spectra of single hyperpolarized samples using this technique, and discuss different options for distributing the polarization among different scans. This robust method takes full advantage of Fourier NMR to resolve overlapping chemical shifts, and may prove particularly useful for the structural elucidation of compounds in mass-limited samples.     

Characterization of magnetic materials by low-field microwave absorption techniques

A low-field non-resonant microwave absorption has recently been observed in a variety of magnetically ordered materials at low DC fields (−1000 Oe H_DC+1000 Oe), which is known as low-field microwave absorption (LFA). It has been shown that LFA is essentially similar to giant magnetoimpedance (GMI), and clearly different from ferromagnetic resonance (FMR). LFA strongly depends on the anisotropy field of the sample. In contrast with FMR (which can be described as the homogeneous precession of spins in the saturated state), LFA can be thought as a spin rotation process occurring during the magnetic saturation. In this work, we present a detailed study of the basic features of LFA in several types of materials: ferrites and amorphous microwires and ribbons; in particular the effects sample shape, temperature up to the Curie transition, the influence of easy axis and the effects of annealings. These examples show that once LFA is fully understood, it can become a powerful characterization tool.     

NMR of water in biological systems

Summary A simple relationship has been thought to exist between the dynamics of water in heterogeneous (liquid-solid) systems and the NMR response. This relationship is usually expressed by the Bloembergen-Purcell-Pound (BPP) equations for relaxation and the phase model. However, a requirement for the use of the BPP theory is that motions take place in an isotropic, infinite and three-dimensional space. It is shown that the mere presence of solid surfaces causes the appearance of solidlike features in the NMR response of the liquid even if its dynamics is directly affected by the surfaces. Some of these ?topological? or ?indirect? surface effects are of the same kind as the low-dimensionality effects. Their order of magnitude is estimated for simple geometries and by treating the liquid motion in a hydrodynamic approximation. Comparison with the experiment is carried on in a companion paper. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

~(141)Pr~ 581.69nm谱线超精细结构光谱研究

利用共线快离子束 激光光谱学方法测量了正一价镨离子波长 5 81.6 9nm谱线的超精细结构光谱 ,得到了超精细相互作用常数 ;与已发表的数据比较 ,在测量误差范围内一致 ,我们的测量精度提高了一个量级     

类氢离子基态超精细结构的理论研究

利用相对论多组态Dirac-Fock方法,系统计算了类氢离子165Ho66+, 185Re74+,187Re74+,207Pb81+, 209Bi82+, 203TI80+和205TI80+的基态超精细结构分裂以及相应的基态跃迁波长,并与相关实验数据及其它理论结果进行了对比.     

The magnetic hyperfine structure in the rotational spectrum of H2CNH

The hyperfine structure in the ground-state rotational spectrum of methanimine was studied in the frequency range of 64-172 GHz by means of the Lamb-dip technique. This allowed to resolve, in some hyperfine components due to the ¹⁴N nucleus, doublets separated by only some tenth of kHz. We explain the splittings as due to magnetic interactions of the three protons with their molecular environment. The analysis of the experimental spectrum has been guided by quantum-chemical calculations of the hyperfine parameters.     

NMR and IR investigations of biologically active peptides in solution

Summary Nuclear-magnetic-resonance and infra-red spectroscopic features in solution have been investigated for the delineation of conformation and dynamics of the chemotactic peptide formyl-L-methionyl-L-leucyl-L-phenylalanine. The main conformation is unfolded and characterized by a certain degree of weak intermolecular hydrogen bounding. The steric hindrance of neighbouring side chains limits the motional averaging of the several possible conformers by excluding some of the rotamers. Dipolar and scalar connectivities, as detected by 2D NMR spectroscopy, point to a cis configuration of the H−N−C−H_α moiety in the case of leucine and trans in the cases of methionine and phenylalanine.

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Riassunto Per il chiarimento della conformazione e della dinamica molecolare del peptide chemotattico formil-L-metionil-L-leucil-L-fenilalanina sono stati studiati i parametri spettroscopici di risonanza magnetica nucleare ed infrarosso in soluzione. La conformazione principale è distesa e caratterizzata da un certo grado di deboli legami a idrogeno intermolecolari. L’impedimento sterico di catene laterali vicine limita la possibilità che i vari conformeri possibili siano mediati dai moti molecolari, escludendo alcuni rotameri. Le connettività dipolari e scalari, messe in evidenza dalla spettroscopia 2D NMR, suggeriscono una configurazione cis del residuo H−N−C−H_α nel caso della leucina e trans nei casi della metionina e della fenila lanina.

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Реэюме Исследуются ядерный магнитный резонанс и инфра-красные спектроскопические характеристики в растворе с целью описания конформации и динамики хемотактичного пептида формия-Л-метионил-Л-лейцил-Л-фенилаланина. Основная конформация явлется раэвернутой и характериэуется определенной степенью слабой межмолекулярной водородной связй. Стерическое припятствие для соседних боковых цепей ограничивает динамическое усреднение для некоторых конформаций, исключая некоторые ротамеры. Дипольнье и скалярные связности, зарегистрированные с помощью 2D ЯМР-спектроскопии, указывают на цис-конфигурацию H−N−C−H_α в случае лейцина и на транс-конфигурацию в случаях метионина и фенилаланина.

     

NMR frequency and magnetic dipole moment of (3)He nucleus

We present new gas-phase NMR spectra which relate the resonance frequency of (3)He nucleus to the resonance frequency of the proton in tetramethylsilane (TMS). We discuss the dependence of (3)He resonance frequency on the density of the solvent gas, and we consider in detail the absolute shielding scales of both nuclei. Finally, we analyse the accuracy of the results, using the relationship between the resonance frequencies, absolute shielding constants and magnetic dipole moments of (1)H and (3)He nuclei.     

A computer algorithm for the simulation of any nuclear magnetic resonance (NMR) imaging method

More than a dozen Nuclear Magnetic Resonance (NMR) imaging methods have been described using different radio-frequency pulse sequences, magnetic field gradient variations, and data processing. In order to have a theoretical understanding in the most general case, we have conceived a computer program for the simulation of NMR imaging techniques. The algorithm uses the solution of the Bloch equations at each point of a simulated object. The direction of every elementary magnetic moment is computed at each instant, and stored in an array giving the global signal to be processed, whatever the pulse and gradient sequence. To test the validity of this program, we have simulated some well-known experimental results. Some applications are presented which contribute to the understanding of image distortions and to techniques such as selective radio-frequency pulse or oscillating gradients. This program can be used to unravel physical and technological causes of image distortions, to have a "microscopic" look at any parameter of an experiment, and to study the contrast given by various NMR imaging techniques as a function of the three NMR parameters, i.e., the hydrogen nuclei density rho and the relaxation times T1 and T2.     

Water dynamics in ionic magnetic colloids studied by H nuclear magnetic resonance

In a previous nuclear magnetic resonance (NMR) study we observed that the NMR spectra of water in both surfacted and ionic ferrofluids are asymmetric and several orders of magnitude wider than the one of pure water. It has been proposed that this effect is produced by extremely strong magnetic field gradients in the intergrain volume and/or by surface interactions between the carrier liquid molecules and the grains surface. In the case of aqueous ionic ferrofluids the latter possibility should be interpreted as electric interactions between water (polar) molecules and the charges in the grain surface.

In this work we study a series of ionic and surfacted ferrofluids prepared at different magnetic grain concentrations and sizes, and with different surface charge densities. Our experiments clearly show that the sign and the density of the electric charge on the magnetic grains have no influence on NMR spectra. On the other hand, spectral widths increase with the magnetic grain concentration.     

Site location and requirements for the installation of a nuclear magnetic resonance scanning unit

The installation of a nuclear magnetic resonance unit in any diagnostic facility involves certain location and environmental requirements. Based on our experience with the FONAR QED 80 system, we have delineated the major factors which must be considered when planning for such an installation. The major requirements are location and space. Suggested layouts for the suite and the control room are included. Certain environmental specifications will vary depending on the location of the facility and the type of unit installed.     

Study of fast switching processes due to electric and magnetic fields-an NMR approach

Solid state NMR techniques have been developed to investigate dynamic molecular effects (e.g., molecular reorientations) due to simultaneously applied external electric fields on electrically sensitive materials such as liquid crystals (LC), liquid crystalline polymers (LCP) and polymeric electrets. Such effects can be observed only on relatively thin systems (10-200 μm). That means that many scans are necessary to achieve a sufficiently high signal-to-noise-ratio in the spectra (500-1000 scans). If the material is also magnetically sensitive, the electric field can be used to orient molecules in a starting orientational state and by switching-off the voltage to access fast reorientation processes in the magnetic field B₀. Until now, the behaviour of orientable molecular systems under the influence of electric fields has been investigated by means of a more or less quasistatic approach (LCP: 100 V, electrets: 1 kV) in equilibrium states. The achievable time resolution depends on the desired signal-to-noise-ratio. For the case of proton NMR this means a time resolution of about 10 min. However, very often switching processes occur on a much shorter time scale. Using conventional techniques it is impossible to observe fast (ca. 100 μs) electrically or magnetically induced reorientation processes. In this work, we present a concept to overcome the problems outlined above and to extend the area of our current in situ NMR investigations on thin electrically-switched or poled polymeric layers. The basic idea is to include synchronized electric pulses during the NMR experiment using the preparation and/or mixing periods of a 1D or 2D pulse sequence for the application of an orienting field (electric or magnetic) and to use the reversibility of the molecular switching phenomenon to achieve a sufficient signal-to-noise-ratio. The techniques extend the range of possible investigations from about 100 μs to approximately T₁ for correlated spectra (and to longer times of applied fields for uncorrelated spectra). Results are shown for a nematic LC and a nematic polymer having a similar side chain.     

Site selection NMR study on electronic state in and near vortex core of YBa2Cu4O8

We report a site-selective ¹⁷O spin-lattice relaxation rate T₁⁻¹ in the vortex state of YBa₂Cu₄O₈. We found that T₁⁻¹ at the planar sites exhibits an unusual nonmonotonic NMR frequency dependence. Based on T₁⁻¹ in the vortex core region, we establish strong evidence that the local density of states within the vortex core is strongly reduced.     

Resolved magnetic hyperfine spectra of Au-Fe alloys as a function of temperature

We have analyzed the Mössbauer hyperfine magnetic spectra of six compositions of Au-Fe from 10.5 to 33 at.% Fe at temperatures ranging from 4.2 K to the magnetic ordering temperature of each alloy. Only two elementary magnetic hyperfine spectra are required to fit the data, each of which has its own value of the magnetic hyperfine field, quadrupole coupling, isomer shift, and relative intensities. The intensity ratios of the two spectra for a given Fe concentration are essentially invariant with temperature. These results point to the existence of two chemically different Fe sites with all the Fe atoms magnetically coupled over the entire temperature regime below the upper magnetic ordering temperature. A relatively sharp increase in the local moment commences at both Fe sites, at ∼ 17 at.% Fe and continues to increase with Fe concentration.     

Electron energy-loss spectroscopy in the low-loss region as a characterization tool of electrode materials

Energy losses below 100 eV are by far less exploited than higher losses in electron energy-loss spectroscopy. Two new examples are given to illustrate the characterization possibilities offered by spectra in this energy range. Typical materials that could be used as electrodes in electrochemical cells were chosen as application cases. Through the use of calculations based on density functional theory, we first demonstrate that the first peak present at the lithium K edge in Li _x TiP₄ can give access to the precise localisation of inserted Li atoms in the f.c.c. structure. In particular, different tetrahedral sites could be differentiated according to their distance to the Ti site. Secondly, calculations of valence electron energy-loss spectra of perovskite materials indicate that a characteristic peak for regular perovskite (Pm m space group) exists in the 10–15 eV range. The high sensitivity of this peak to the distortion of the octahedron arrangements is also demonstrated. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

NMR magnetization transfer as a tool for characterization of nanoporous materials

The application of nuclear magnetic resonance magnetization transfer experiments to probe the surface-to-volume ratio and pore morphology of porous materials with characteristic pore sizes of 1-100 nm is described. The method is based on the phenomenon of incomplete freezing of liquids in small pores where a few monolayers adjacent to the pore walls remain liquid. Sufficient difference between the transverse relaxation times in the solid frozen core and liquid surface layer allows the initial preparation and subsequent re-equilibration of a solid-liquid magnetization grating. The method is demonstrated using model nanoporous materials with known characteristics. The ensuing problems of the mechanism of the magnetization transfer through the interface and within the frozen core are discussed and elucidated by pulsed-field-gradient NMR experiments.