Multiple-rotor-cycle 2D PASS experiments with applications to (207)Pb NMR spectroscopy

Thetwo-dimensional phase-adjusted spinning sidebands (2D PASS) experiment is a useful technique for simplifying magic-angle spinning (MAS) NMR spectra that contain overlapping or complicated spinning sideband manifolds. The pulse sequence separates spinning sidebands by their order in a two-dimensional experiment. The result is an isotropic/anisotropic correlation experiment, in which a sheared projection of the 2D spectrum effectively yields an isotropic spectrum with no sidebands. The original 2D PASS experiment works best at lower MAS speeds (1-5 kHz). At higher spinning speeds (8-12 kHz) the experiment requires higher RF power levels so that the pulses do not overlap. In the case of nuclei such as (207)Pb, a large chemical shift anisotropy often yields too many spinning sidebands to be handled by a reasonable 2D PASS experiment unless higher spinning speeds are used. Performing the experiment at these speeds requires fewer 2D rows and a correspondingly shorter experimental time. Therefore, we have implemented PASS pulse sequences that occupy multiple MAS rotor cycles, thereby avoiding pulse overlap. These multiple-rotor-cycle 2D PASS sequences are intended for use in high-speed MAS situations such as those required by (207)Pb. A version of the multiple-rotor-cycle 2D PASS sequence that uses composite pulses to suppress spectral artifacts is also presented. These sequences are demonstrated on (207)Pb test samples, including lead zirconate, a perovskite-phase compound that is representative of a large class of interesting materials.     

Magnetic resonance imaging of objects with dipolar-broadened spectra using soft excitation pulses

Feasibility of acquiring high-resolution 3D NMR images of objects with dipolar-broadened spectra by using soft excitation pulses is experimentally demonstrated. The models are liquid-crystalline phantoms and a pencil eraser. The pulse sequence is a standard 3D gradient-echo sequence.     

A simple scheme for probehead background suppression in one-pulse 1H NMR

A very simple method for reducing probehead background signal in one-pulse 1H nuclear magnetic resonance (NMR) spectra is presented. Two one-pulse spectra are recorded, the first with pulse length tp1, the second with an L-times longer pulse, e.g. with L = 2. The second spectrum scaled by 1/L is subtracted from the first. Since the weak pulses experienced by spins outside the coil are in the linear regime, the background from outside the coil is effectively subtracted out. The background suppression efficiency is approximately 1.5b2, where b is the ratio of the B1 field inside the coil relative to that outside the coil. Experimentally, background suppression by at least a factor of 10 was achieved. Examples of background suppression in 1H wideline as well as 1H fast magic-angle spinning (MAS) one-pulse spectra of clay and polymer samples are shown.     

High-resolution solid-state 119Sn and 195Pt NMR studies of MPtSn semiconductors (M = Ti, Zr, Hf, Th)

Solid-state 119Sn and 195Pt magic-angle spinning (MAS) NMR spectra are reported on a series of MPtSn compounds (M = Ti, Zr, Hf, Th). In favorable cases (TiPtSn and ZrPtSn) the spectra reveal expected J-coupling patterns originating from indirect spin coupling between Pt and Sn nuclei. MAS has no effect on the broad and asymmetric spectra of either 119Sn and 195Pt nuclei in HfPtSn.     

Double-quantum filtered MAS NMR in the presence of chemical shielding anisotropies and direct dipolar and J couplings

Double-quantum filtered MAS NMR spectra of an isolated homonuclear spin-1/2 pair are considered, at and away from rotational resonance conditions. The pulse sequence used is the solid-state NMR equivalent of double-quantum filtered COSY, known from solution-state NMR. The 119Sn spin pair in [(chex3Sn)2S] is characterized by a difference in isotropic chemical shielding smaller than the two chemical shielding anisotropies and by direct dipolar and isotropic J-coupling constants of similar magnitudes. At rotational resonance, one-dimensional double-quantum filtered 119Sn lineshapes yield the relative orientation of the two 119Sn chemical shielding tensors. Good double-quantum filtration efficiencies are found at and away from rotational resonance conditions, despite the presence of large chemical shielding anisotropies. Numerical simulations illustrate the interplay of the direct dipolar and J-coupling pathways and identify the latter as the main pathway even at rotational resonance conditions.     

Spectral parameters for quantitative mobility contrast in NMR imaging of solid polymers

Different procedures based on parameters of the wideline NMR absorption spectrum are presented to obtain localized molecular mobility contrast for imaging of solid polymers. For this purpose a ¹H-NMR imaging technique with magic sandwich echoes is used for acquiring localized wideline spectra. With samples composed of polystyrene and high impact strength polystyrene, and polycarbonate and low density polyethylene a spatial difference in NMR absorption spectrum lineshape and linewidth is displayed. Furthermore, the spatial distribution of rigid and mobile domains in a heterogeneous polymer can be derived from the NMR spectral components. It is demonstrated that a van Vleck moment analysis can be performed from spatially resolved magic echo decays. The second (M₂) and fourth (M₄) moments of the rigid components show considerable variation with the spatial composition of the investigated samples.     

Experimental study of the amorphous phases of group-IV semiconductors by the119mSn Mössbauer probe

The amorphous phases of silicon, germanium, and -tin have been studied by Mössbauer emission spectroscopy on ion-implanted, radioactive^119mSn. Amorphous samples have been produced by ion implantations of various elements and by vacuumevaporation techniques. The same well-defined type of complex spectrum is observed for all investigated amorphous samples. These spectra are characterized by an increase in average isomer shift of (0.15±0.03) mm/s, a line broadening of 20±2%, and the same Debye temperature as compared with spectra of substitutional Sn in the respective crystalline host lattices. The spectra are proposed to originate from Sn atoms incorporated substitutionally in the amorphous host with distorted local surroundings. The recrystallization of the amorphous phase upon thermal and laser annealing has been monitored. After appropriate annealing, spectra characteristic of crystalline materials are observed for most samples. An exception are high-dose, inert-gas implanted samples where different complex defects seem to be formed in the annealing process.     

Efficient 5QMAS NMR of spin-5/2 nuclei: use of fast amplitude-modulated radio-frequency pulses and cogwheel phase cycling

We report here an efficient multiple-quantum magic-angle spinning (MQMAS) pulse sequence involving fast amplitude-modulated (FAM) radio-frequency pulses for excitation and conversion of five-quantum (5Q) coherences of spin-5/2 nuclei. The use of a FAM-I type pulse train for the conversion of 5Q into 1Q coherences proves to be easier to implement experimentally than the earlier suggested use of a FAM-II type sequence [J. Magn. Reson. 154 (2002) 280], while delivering at least equal signal enhancement. Results of numerical simulations and experimental 27Al 5QMAS spectra of aluminium acetylacetonate for different excitation and conversion schemes are compared to substantiate these claims. We also demonstrate the feasibility of acquiring 5QMAS spectra of spin-5/2 systems using cogwheel phase cycling [J. Magn. Reson. 155 (2002) 300] to select the desired coherence pathways. A cogwheel phase cycle of only 57 steps is shown to be as effective as the minimum conventional nested 77-step phase cycle.     

Solid state 31P and 207Pb MAS NMR studies on polycrystalline O,O'-dialkyldithiophosphate lead(II) complexes

A number of lead(II) O,O'-dialkyldithiophosphate complexes were studied by (13)C, (31)P, and (207)Pb MAS NMR. Simulations of (31)P chemical shift anisotropy using spinning sideband analysis reveal a linear relationship between the SPS bond angle and the principal values delta(22) and delta(33) of the (31)P chemical shift tensor. The (31)P CSA data were used to assign ligands with different structural functions. In the cases of diethyldithiophosphate and di-iso-butyldithiophosphate lead(II) complexes, (2)J((31)P, (207)Pb)-couplings were resolved and used to confirm the suggested assignment of the ligands. The SIMPSON computer program was used to calculate (31)P and (207)Pb spectral sideband patterns.     

119Sn Mössbauer Study of as-Deposited Layers Prepared by Co-evaporation of TeO2 and Sn

The deposited layers on glass surface with thickness between 230 and 500 nm were prepared by the chemical reactions of TeO₂ and Sn during vacuum co-deposition, and were characterized as a function of the Sn/Te ratio between 0.5 and 2.8 by ¹¹⁹Sn conversion electron Mössbauer spectroscopy. The as-deposited samples showed amorphous character with very finely dispersed microstructure. The ¹¹⁹Sn Mössbauer spectra of as-deposited samples revealed the dominance of Sn(II) and Sn(IV) states although SnTe was also found when the Sn/Te ratio was high. A monotonous increase of the Sn(II)/Sn(IV) ratio was observed with increasing Sn/Te ratio.     

Mössbauer spectroscopy of laser annealed tellurium implanted silicon (I).119Sn and125Te

Laser annealed Te-implanted silicon has been investigated using¹¹⁹Sn and¹²⁵Te Mössbauer spectroscopy. The¹¹⁹Sn Mössbauer spectra consist of a single lorentzian, known to be due to substitutional Sn atoms in Si, independent of the type of doping of the silicon. The results on¹²⁵Te revcal at least two different components. In heavily doped n-type Si a single line component is observed with an isomer shift of 0.15 (5) mm/s with respect to SnTe and an effective Debye temperature of 207 (3) K. Heavy p-doping leads to another single line component with an isomer shift of ?0.13 (5) mm/s and an effective Debye temperature of 232 (3) K. These components are ascribed to the neutral and doubly positive charge state of substitutional Te atoms, respectively.     

Laser ablation fast pulse discharge plasma spectroscopy analysis of Pb,Mg and Sn in soil

Laser ablation fast pulse discharge plasma spectroscopy (LA-FPDPS) technique is a recently developed atomic emission analytical technique that is analogous to dual pulse laser induced breakdown spectroscopy (DP-LIBS). LA-FPDPS, however, uses a periodical oscillating discharge plasma generation method on samples instead of the second laser beam in DP-LIBS. Here we describe the electric characteristics and its application to the analysis of Pb, Mg and Sn in soil. Due to the fast discharge process, the peak power deposition rate is up to 1.5 MW, although the discharge energy is relatively small. The main energy deposition process only last for ~ 4 μs. From the measured spectra, calibration curves for Pb, Mg and Sn in soil were derived and the limits of detection were 1.5 μg/g, 34 μg/g and 0.16 μg/g respectively.     

Simultaneous measurement of beta- decay to bound and continuum electron states

We report the first measurement of a ratio lambda(beta(b))/lambda(beta(c)) of bound-state ((lambda(beta(b))) and continuum-state (lambda(beta(c))) beta(-)-decay rates for the case of bare 207Tl81+ ions. These ions were produced at the GSI fragment separator FRS by projectile fragmentation of a 208Pb beam. After in-flight separation with the Brho-deltaE-Brho method, they were injected into the experimental storage-ring ESR at an energy of 400.5A MeV, stored, and electron cooled. The number of both the 207Tl81+ ions and their bound-state beta(-)-decay daughters, hydrogen-like 207Pb81+ ions, were measured as a function of storage time by recording their Schottky-noise intensities. The experimental result, lambda(beta(b))/lambda(beta(c)) = 0.188(18), is in very good agreement with the value of 0.171(1) obtained from theory employing spectra of allowed transitions.     

Assignment of congested NMR spectra: carbonyl backbone enrichment via the Entner-Doudoroff pathway

In NMR spectra of complex proteins, sparse isotope enrichment can be important, in that the removal of many (13)C-(13)C homonuclear J-couplings can narrow the lines and thereby facilitate the process of spectral assignment and structure elucidation. We present a simple scheme for selective yet extensive isotopic enrichment applicable for production of proteins in organisms utilizing the Entner-Doudoroff (ED) metabolic pathway. An enrichment scheme so derived is demonstrated in the context of a magic-angle spinning solid-state NMR (MAS SSNMR) study of Pf1 bacteriophage, the host of which is Pseudomonas aeruginosa, strain K (PAK), an organism that uses the ED pathway for glucose catabolism. The intact and infectious Pf1 phage in this study was produced by infected PAK cells grown on a minimal medium containing 1-(13)C d-glucose ((13)C in position 1) as the sole carbon source, as well as (15)NH(4)Cl as the only nitrogen source. The 37MDa Pf1 phage consists of about 93% major coat protein, 1% minor coat proteins, and 6% single-stranded, circular DNA. As a consequence of this composition and the enrichment scheme, the resonances in the MAS SSNMR spectra of the Pf1 sample were almost exclusively due to carbonyl carbons in the major coat protein. Moreover, 3D heteronuclear NCOCX correlation experiments also show that the amino acids leucine, serine, glycine, and tyrosine were not isotopically enriched in their carbonyl positions (although most other amino acids were), which is as expected based upon considerations of the ED metabolic pathway. 3D NCOCX NMR data and 2D (15)N-(15)N data provided strong verification of many previous assignments of (15)N amide and (13)C carbonyl shifts in this highly congested spectrum; both the semi-selective enrichment patterns and the narrowed linewidths allowed for greater certainty in the assignments as compared with use of uniformly enriched samples alone.     

Calibration of the isomer shift of119Sn from internal conversion measurement

Radioactive¹¹⁹Sb was implanted into 6 different host matrices, Y, Β-Sn, Pt, Au, Pb and CaSnO₃, and internal-conversion and Mössbauer spectra were measured for the same samples. The isomer-shift calibration constant of the Mössbauer transition of¹¹⁹Sn was derived as δR/R=(0.87±0.25)×10^?4 for R=1.2×A^1/3 fm or, δ〈r²〉=(3.6±1.0)×10^?3 fm².     

Crossing fibers, diffractions and nonhomogeneous magnetic field: correction of artifacts by bipolar gradient pulses

In recent years, diffusion tensor imaging (DTI) and its variants have been used to describe fiber orientations and q-space diffusion MR was proposed as a means to obtain structural information on a micron scale. Therefore, there is an increasing need for complex phantoms with predictable microcharacteristics to challenge different indices extracted from the different diffusion MR techniques used. The present study examines the effect of diffusion pulse sequence on the signal decay and diffraction patterns observed in q-space diffusion MR performed on micron-scale phantoms of different geometries and homogeneities. We evaluated the effect of the pulse gradient stimulated-echo, the longitudinal eddy current delay (LED) and the bipolar LED (BPLED) pulse sequences. Interestingly, in the less homogeneous samples, the expected diffraction patterns were observed only when diffusion was measured with the BPLED sequence. We demonstrated the correction ability of bipolar diffusion gradients and showed that more accurate physical parameters are obtained when such a diffusion gradient scheme is used. These results suggest that bipolar gradient pulses may result in more accurate data if incorporated into conventional diffusion-weighted imaging and DTI.     

Proton decay of the isobaric analogs of the ground states of207Pb and208Pb

The proton decays \(\tilde p\) of isobaric analog states of^{207, 208}Pb in the reactions^{207, 208}Pb(p, n) have been studied using a neutron-proton coincidence technique. The width anomaly observed in (p, n) [4] and (p, n \(\tilde p\) ) singles spectra [11] is resolved in the coincident spectra.     

Selective saturation in strongly inhomogeneous magnetic fields

The possibility to produce selective saturation by nuclear magnetic resonance (NMR) sequences of low-power radio-frequency pulses in strongly inhomogeneous magnetic fields is explored. The saturation of parts of the sensitive volume is produced by a particular pulse sequence with reduced amplitude distribution and the spectrum of the recorded signal is compared with the simulated spectrum. The spectra of the recorded free induction decays and echo signals are in good agreement with the simulated spectra of the pulse sequence, which demonstrates the effect of the selective saturation. The results obtained are an important step towards the development of new mobile and lowpower NMR equipments operating with inhomogeneous magnetic fields.     

Defect structures of ion-implanted α-tin

Single crystalline and polycrystalline -tin has been implanted at room temperature with 80-keV ions of radioactive^119m Sn,¹¹⁹Sb, and^119m Te. The radioactive nuclei decay to the Mössbauer level of¹¹⁹Sn. Mössbauer spectra of the emitted 24-keV radiation have been measured for different source temperatures by resonance counting techniques. Five individual lines in the spectra are characterized mainly by their isomer shifts and Debye temperatures. From these parameters the radiogenic¹¹⁹Sn atoms are concluded to be located in regular substitutional and interstitial lattice sites and in defect complexes. Simple models for the defects are proposed: A Sn-vacancy pair consists of Sn atoms on (nearly) substitutional sites with a dangling bond into an adjacent vacancy. In a complex oxygen-containing defect the Sn atoms have approximately a 5s ² configuration withp-bonds to two nearest neighbour atoms. Sn atoms, having an atomic 5s ² 5p ² configuration and large vibrational amplitudes, are concluded to be in non-bonding regular interstitial sites. For special implantation conditions minor fractions of SnO₂ molecules are formed in the bulk. The interstitial¹¹⁹Sn and the¹¹⁹Sn-vacancy pairs are proposed to represent elementary point defects in -tin. Conclusions are also drawn concerning the lattice location and the defects created in the implantation process of the implanted parent isotopes.