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B Blümich

Publications and source records attributed to B Blümich.

At least 19 recordsLinked to original sources

Double-quantum-filtered NMR signals in inhomogeneous magnetic fields.

The possibility of exciting and detecting proton NMR double-quantum coherences in inhomogeneous static and radiofrequency magnetic fields was investigated. For this purpose specialized pulse sequences which partially refocus the strongly inhomogeneous evolution of the spin system and generate double-quantum buildup and decay curves were implemented on the NMR MOUSE (mobile universal surface explorer). The theoretical justification of the method was developed for the simple two-spin-1/2 system. The performances of the same pulse sequences were also tested on a solid-state high-field NMR spectrometer. It was shown that DQ decay curves have a better signal-to-noise ratio in the initial time regime than DQ buildup curves. The double-quantum buildup and decay curves were recorded for a series of cross-linked natural rubber samples. These curves give access to quantitative values of the ratio of proton total residual dipolar couplings which are in good agreement with those measured in homogeneous fields. A linear dependence of these ratios on the sulfur-accelerator content was found.

Journal Article↗

Dipolar and J encoded DQ MAS spectra under rotational resonance.

A two-dimensional (2D) double-quantum (DQ) experiment under rotational resonance (R(2)) conditions is introduced for evaluating dipolar couplings in rotating solids. The contributions from the R(2)-recoupled dipolar interaction and the J coupling can be conveniently separated in the resulting 2D R(2)-DQ spectrum, so that the unknown dipolar coupling can readily be extracted, provided that the values of the involved J coupling constants are known. Since the measured parameters are integral intensity ratios between suitably chosen absorption peaks in the 2D spectrum, the proposed method is characterized by a reduced sensitivity to relaxation parameters. The effect of rotor-modulated terms, including chemical shift anisotropy, is efficiently averaged out by synchronizing the excitation/reconversion time with the rotor period. All of these features are demonstrated theoretically by the example of two model systems, namely, isolated spin-pairs and a three-spin system. The results of the theoretical models are applied to both (13)C and (1)H nuclei to extract dipolar couplings in uniformly (13)C labeled L-alanine and a crosslinked natural rubber.

Journal Article↗

One-dimensional imaging with a palm-size probe.

A new portable magnetic resonance imaging device was built. Spatially resolved NMR was achieved by placing a gradient coil pair and a Helmholtz pair type radio-frequency probe in the gap between two antiparallel polarized permanent magnets. The flat face of the low-field (nu(proton) = 20 MHz) apparatus allowed for the study of arbitrarily large objects in situ. Relaxation time weighted 1D images were achieved over a 15-mm field of view by a single-point spin-echo sequence. A phase encoding time on the order of 200 micros permited the scanning of a wide range of heterogeneous materials.

Cost-Benefit Analysis↗

Anisotropy in tendon investigated in vivo by a portable NMR scanner, the NMR-MOUSE.

Ordered tissue like tendon is known to exhibit the magic-angle phenomenon in magnetic resonance investigations. Due to the anisotropic structure the transverse relaxation time T(2) depends on the orientation of the tendon in the magnetic field. In medical imaging, relaxation measurements of tendon orientation are restricted by the size of the object and the space available in the magnet. For humans, tendon orientation can only be varied within small limits. As a consequence, the magic-angle phenomenon may lead to a misjudgement of tendon condition. It is demonstrated that the NMR-MOUSE (mobile universal surface explorer), a hand-held NMR sensor, can be employed to investigate the anisotropy of T(2) in Achilles tendon in vivo. The NMR-MOUSE provides a convenient tool for analyzing the correlation of T(2) and the physical condition of tendon.

Achilles Tendon↗

Comparative study of motions in dimethylsulfone by noise excitation and solid echo spectroscopy.

2H NMR spectra of dimethylsulfone were measured with noise excitation and solid echo NMR spectroscopy in the temperature range from 125 to 355 K. Besides the known fact that broad NMR spectra can be measured with both methods, in comparable times it is shown that for noise excitation, the signal loss is negligible compared to echo spectroscopy in the regime when the correlation times of the motions are of the order of magnitude of the echo pulse spacing. For simulating the dynamic NMR spectra acquired with noise excitation, only the motional process must be taken into account and relaxation can be neglected. Furthermore, the problem of restricted acquisition bandwidth in noise NMR spectroscopy is discussed.

Cold Temperature↗

1H NMR imaging of residual dipolar couplings in cross-linked elastomers: dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum filters.

Contrastfilters for NMR imaging of residual 1H dipolar couplings of elastomers are introduced based on dipolar-encoded longitudinal magnetization, as well as double- and triple-quantum coherences. The spin response is discussed in the initial excitation time regime for methylene, methyl, and methine protons applicable to poly(isoprene) and other elastomers, taking into account the hierarchy of dipolar couplings and the associated editing features of multiple-quantum experiments. The efficiency of these filters is investigated for a series of cross-linked poly(isoprene) samples. Spatially resolved dipolar-encoded longitudinal magnetization decays and double-quantum and triple-quantum buildup curves are presented for a phantom made of poly(isoprene) with different cross-link densities. Two-dimensional images representing residual dipolar couplings are presented using dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum contrast filters. Images from dipolar-encoded longitudinal magnetization and triple-quantum coherences show the highest resolution and contrast, respectively.

Algorithms↗

Proton residual dipolar couplings by NMR magnetization exchange in cross-linked elastomers: determination and imaging.

Proton nuclear magnetic resonance (NMR) magnetization exchange is used to investigate residual dipolar couplings in a series of cross-linked poly(styrene-cobutadiene) elastomers. A new model for the dipolar unit is used for the evaluation of the signal decay in magnetization exchange experiments. It takes into account an extended residual dipolar coupling network along the polymer chain. It is shown that in the regime of short mixing times, information about the residual dipolar coupling between methine and methylene protons can be obtained which is not affected by other inter- and intramolecular dipolar couplings. The dynamic order parameter of methine-methylene protons is measured and correlated with cross-link density. This study certifies the quality of a filter for magnetization from residual dipolar couplings which exploit magnetization exchange. The filter can be used to generate contrast in NMR images of heterogeneous elastomers. The first proton NMR parameter image of a dynamic order parameter is presented for a phantom made from poly(styrene-cobutadiene) samples with different cross-link densities.

Algorithms↗

Analysis of polymer materials by surface NMR via the MOUSE.

Applications are discussed of a novel NMR device, the NMR MOUSE (mobile universal surface explorer), for characterization of polymers. Different properties of elastomers can be related to an effective transverse relaxation parameter T2eff. Effects of multi-echo sequences influence the decay curve and can be described in terms of B0 inhomogeneity and spin-lock effects. Furthermore, the signal-to-noise ratio (SIN) can be improved by use of steady-state free precession (SSFP) pulse sequences modified for use in inhomogeneous magnetic fields.

Magnetic Resonance Spectroscopy↗

Characterization of cross-link density in technical elastomers by the NMR-MOUSE.

NMR is a powerful tool in characterizing cross-link density in elastomers. Conventional NMR, however, restricts the sample geometry and does not allow measurements in presence of ferromagnetic materials. The concept of the MOUSE (mobile universal surface explorer) circumvents these restrictions. This surface sensitive method deals with rather inhomogeneous magnetic fields instead of the highly homogeneous fields normally used in NMR. Therefore, pulse sequences are reinvestigated with respect to their sensitivity towards residual dipolar coupling in elastomers. Examples for investigations of technical elastomers and correlations of NMR results with data from macroscopic mechanical measurements are presented.

Macromolecular Substances↗

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.

Chemical Phenomena↗

The influence of molecular motion on cross-polarization in cross-linked elastomers.

The effect of molecular motion on the heteronuclear cross-polarization rate for the case of the spin-lock procedure was investigated. In applying heteronuclear solid state NMR techniques to mobile elastomer systems the influence of molecular motion cannot be neglected. Starting in the slow motion regime a strong collision model was used for predicting changes of the cross-polarization rate in the dipolar spectral density function of abundant spins. The dipolar correlation time and hence the cross-polarization rate is found to scale with the inverse of the correlation time of the molecular motion. The same behavior is obtained using a second approach valid in the intermediate molecular motion regime. This is based on the effect of the motion on the homonuclear and heteronuclear van-Vleck moments and leads to a linear dependence of the cross-polarization rate on the correlation time of molecular motion. This dependence was verified experimentally by 1H-13C high-resolution cross-polarization measurements on sulfur cross-linked elastomer systems. 13C rotating frame spin-lattice relaxation rate measurements were used to corroborate these data and the approximations used to evaluate the influence of molecular motion on cross-polarization rates. The dependence of these rates on the cross-link density of the elastomer network is analyzed and it is shown that they scale with the cross-link density. The correlation of the 1H-13C cross-polarization rates with the dynamic storage moduli was demonstrated.

Chemical Phenomena↗

Spatially resolved solid-state MAS-NMR-spectroscopy.

A comprehensive account of spatially resolved solid-state MAS NMR of 13C is given. A device generating field gradients rotating synchronously with the magic angle spinner is described. Spatial resolution and sensitivity are compared for phase and frequency encoding of spatial information. The suppression of spinning sidebands is demonstrated for both cases. Prior knowledge about the involved materials can be used for the reduction of data from spatially resolved spectra to map chemical structure. Indirect detection via 13C NMR gives access to the information about mobility from proton-wideline spectra. Two-dimensional solid-state spectroscopy with spatial resolution is demonstrated for a rotor synchronized MAS experiment which resolves molecular order as a function of space. By comparison of different experiments the factors affecting the spatial resolution are investigated.

Carbon Isotopes↗

Hadamard NMR imaging with slice selection.

Stochastic NMR imaging is one of the less common NMR imaging techniques. Nevertheless, stochastic rf excitation is characterized by some remarkable features: the rf excitation power is at least two orders of magnitude lower in comparison to conventionally pulsed NMR imaging schemes. Thus, the technique is of interest for imaging of large objects. The systematic noise inherent in images obtained with random noise excitation has been eliminated by using pseudorandom noise together with Hadamard transformation for data evaluation. Data acquisition times are comparable to those of ultrafast imaging techniques. For slice selection, z magnetization is destroyed outside the slice region with specially designed low power pulses. Thus, gradient switching times are only limited by T1 and not T2*. Images are reconstructed by the backprojection algorithm. We have set up a stochastic imaging procedure on a conventional Bruker MSL 300 spectrometer, and have drawn a comparison between images obtained by the pseudorandom noise excitation and by conventional Fourier imaging.

Fourier Analysis↗

Spatially resolved NMR of rigid polymers and elastomers.

NMR imaging with protons is becoming a more and more versatile tool for material research. Two different approaches are presented to obtain spatial resolution in elastomers and solids. The first, magic-sandwich-echo-imaging, belongs to the group of multiple-pulse techniques which are applied to overcome the strong dipolar couplings in solids. A driver for fast gradient pulses was constructed, and the technique was used to measure one-dimensional projections and spatially resolved spectra of rigid polymers. The second approach uses surface coils. In this way large objects can be investigated from the surface at optimum signal to noise. The drawback of the inhomogeneous B1 field resulting in signal attenuation across the image can be overcome by imaging an NMR parameter like the relaxation time T2. This was applied to image a phantom of different polyurethane foams. Furthermore spin-echo images of signal intensity maps around conducting wires are presented for the analysis of current distributions.

Magnetic Resonance Imaging↗

Application of nuclear magnetic resonance magic sandwich echo imaging to solid polymers.

A solid-state 1H nuclear magnetic resonance (NMR) imaging technique based on magic sandwich echoes (MSE) is described for obtaining spatial projections of solid polymer samples. The modification of MSE multiple echo detection is combined with short gradient pulses applied during the sandwich windows. This allows proton homonuclear decoupling in solids with dipolar couplings up to 50 kHz. For a rapid gating of the gradients a fast gradient pulse driver was constructed with switching times between 550 and 910 ns giving a maximum gradient strength of 330 mT/m. With our detection technique the spectral width can be doubled. One-dimensional projections and spatially resolved spectra of rigid polymer phantoms are presented. For contrast enhancement the use of the T1 relaxation time and the number of the magic sandwiches functioning as an adjustable magnetization filter discriminating between different strengths of the dipolar coupling is demonstrated.

Echo-Planar Imaging↗

Two-dimensional one-pulse rotational echo spectra.

Recently a two-dimensional representation of one-dimensional spinning sideband magic-angle spinning (MAS) spectra has been published with applications to deuteron MAS nuclear magnetic resonance (NMR). The introduction of a new time axis, based on the rotor period, allows the separation of isotropic and anisotropic chemical shifts. It is shown here that, in addition to untangling spinning sideband spectra, data-processing steps can be incorporated which enabled applications of the method to signals from nuclei with anisotropies smaller than those of the quadrupole coupling of deuterons. This is achieved by linear prediction of the rotary echo signals. Advantages and limitations of the algorithm are discussed and demonstrated with experimental results of 13C cross-polarization (CP) MAS spectra of glycine.

Algorithms↗

[In vitro NMR spectroscopy of healthy, pathologically changed and carcinomatous breast tissue samples correlated with histological findings].

Of 57 patients with clinically suspected mamma carcinoma 121 samples were analysed by in vitro 1H-NMR spectroscopy at 300 MHz and correlated with histological data. Within the relevant spectral region between 2.7 and 4.1 ppm strong signals were observed from fat, (phosphoryl-) choline, (phospho-) creatine, and carnitine. Furthermore, with high regularity, 8 weak, partly overlapping signals were resolved and attributed to glucose, glycine, threonine, serine, inositol, and sucrose. Their intensities were determined by an iterative fitness program. From the intensity ratios, different kinds of tissue could be distinguished based on spectroscopic criteria. Healthy or mastopathically modified tissue could be discriminated from more than 50% carcinoma affected tissue with a specificity of better than 99.5%. This fact is explained by the lower content of fatty acids in the malignant tissue. Differences between spectra of healthy of mastopathically affected tissue were only small.

Breast↗

Spinning sidebands from chemical shift anisotropy in 13C MAS imaging.

Solid state imaging by 13C MAS imaging is described. The spinning sidebands occurring at moderate spinning speeds, which disturb the images, can be suppressed by TOSS. For rigid solids the spatial resolution that can be achieved in this way is better than that of 1H images at the same spinning speed. Spatially resolved spectra with or without spinning sidebands can likewise be recorded providing information about the isotropic and the anisotropic chemical shifts which can be exploited for the study of structure, order and dynamics. The techniques are demonstrated on a phantom made with 13C-labelled glycine.

Anisotropy↗