Characteristic times of relaxation peaks of magnetic fluids

The use of the Fokker–Planck equation in theoretical studies of relaxation processes in single-domain particle systems is a well-established technique. However this method has a particular disadvantage in that it can give analytical results solely in some limiting cases. An alternative method, which avoids this difficulty, is that of the use of the integral relaxation time, τ_int, which is presented in this work.     

DOUBLESLICING: a non-iterative single profile multi-exponential curve resolution procedure. Application to time-domain NMR transverse relaxation data

A new non-iterative curve resolution technique for resolving single decay profiles is proposed. The new technique, called DoubleSlicing, is based on the Decra (Direct Exponential Curve Resolution Algorithm) principle. While the original Decra was designed to resolve several decay curves simultaneously and thus fitting common pure exponentials, DoubleSlicing can resolve single decay profiles by a simple double data transformation followed by an analytical and unique three-way decomposition. The new approach is successfully demonstrated on experimental NMR CPMG relaxation data, measured on combinations of unmixed paramagnetic CuSO(4) solutions. Decay signals of the water component were acquired following an innovative experimental design that ensured no interaction between the components present in each sample under observation. DoubleSlicing proved to be accurate in estimating relaxation times differing in one order of magnitude (range: 19.6-159.4ms). Its performance was comparable to discrete exponential fitting with the advantage of being much faster - in terms of computation time, DoubleSlicing outperformed exponential fitting by a factor of four.     

Proton relaxation NMR study of polycrystalline progesterone.

Polycrystalline progesterone (4-pregnene-3,20-dione, C21H30O2) has been investigated by proton NMR methods between 80 and 350 K. A reduction in dipolar second moment is ascribed to methyl group reorientation. Minima in the spin-lattice relaxation time found in measurements at five frequencies from 7 to 200 MHz are attributed to reorientation of two of the three methyl groups in each molecule, characterized by activation energy Ea = 10.9 +/- 0.8 kJ/mol and tau o = (2.3 +/- 0.2) x 10(-13) s. Additional relaxation at lower temperatures is attributed to reorientation of the third methyl group with Ea approximately 3.4 kJ/mol. Measurements were also made of relaxation in the rotating frame.     

利用地球磁场测量质子的自旋弛豫时间

利用地球磁场核磁共振(EF NMR)的方法测量水中质子自旋弛豫的时间.两种不同的自旋弛豫时间T_1和T_2分别测得为(2.46±0.16)s和(0.83±0.02)s,与《Measurement Science and Technology》2012年(21卷)第10期上Michal CA一文所得到的结果T_1=2.3±0.1 s吻合较好.此外,实验数据也验证了居里定律,并通过对硫酸铜溶液的测量说明了溶液中离子的存在会使自旋弛豫过程加快.此工作提供了一种利用地球磁场测量秒量级的自旋弛豫时间的方法.     

Broadening effects on the mass resolution of metastable peaks

The mass resolution achieved for daughter ions resulting from metastable ion reactions in the first field-free region of a double-focussing mass spectrometer is less than that for the main-beam daughter ions. A Monte-Carlo computer program that simulates a mass spectrometer has been used to show that the occurrence of the reactions at points in the first field-free region other than at the fast-sector object slit can give rise to such broadening of the metastable peaks.     

Multi-exponential relaxation analysis with MR imaging and NMR spectroscopy using fat-water systems

This study was undertaken to evaluate the feasibility of multiexponential relaxation data analysis to MR imaging techniques. The first part of this study contains accurate relaxation time measurements performed on a conventional spectrometer. In the second part, essentially the same measuring techniques were applied but now on standard whole body MR imaging equipment. T2 relaxation was measured using multi-echo techniques, T1 relaxation using multiple inversion recovery measurements. Manganese chloride solutions were used for verification of the single exponential model. Water and fat mixtures were considered for multi-exponentiality. Pure fat showed an intrinsic two-exponentiality in T1 and T2 relaxation. Mixtures of fat and water were analyzed and could at best be characterized by two exponentials, although at least three exponentials were known to be present. From the two-exponential fit the relative amounts of fat and water were calculated and compared with the mixture composition. Statistical criteria are discussed to discriminate between single and double exponential behavior in relaxation curves. It is concluded that the time consuming IR measurements for the determination of multiple T1 relaxation are not applicable in a clinical environment. Multiple T2 relaxation can be determined in a reasonable amount of time using multiple echo measurements in one image acquisition. It is shown that the observed values of T1 and T2 from tissues with intrinsic multiexponential relaxation behavior, measured with MR imaging or MR relaxation techniques on a whole-body imager or a conventional spectrometer, depend strongly on the way the experiments are set up and on the model accepted for data analysis.     

Measuring the longitudinal NMR relaxation rates of fast relaxing nuclei using a signal eliminating relaxation filter

A new experiment for selective determination of the relaxation rates of fast relaxing NMR signals is presented. The experiment is derived from the conventional inversion recovery experiment by substituting the 180 degrees inversion pulse of this experiment with a signal eliminating relaxation filter (SERF) consisting of three 180 degrees pulses separated by two variable delays, Delta1 and Delta2. The SERF experiment allows a selective suppression of signals with relaxation rates below a given limit while monitoring the relaxation of faster relaxing signals. The experiment was tested on a sample of 20% oxidized plastocyanin from Anabaena variabilis, where the fast exchange of an electron between the reduced (diamagnetic) and the oxidized (paramagnetic) form results in a series of average signals with widely different relaxation rates. To ensure an optimum extraction of information from the experimental data, the relaxation rates were obtained from the SERF experiment by a simultaneous analysis of all the FIDs of the experiment using a fast linear prediction model method developed previously. The reliability of the relaxation rates obtained from the SERF experiment was confirmed by a comparison of the rates with the corresponding rates obtained from a conventional inversion recovery experiment.     

High resolution 1H NMR of a lipid cubic phase using a solution NMR probe

The cubic mesophase formed by monoacylglycerols and water is an important medium for the in meso crystallogenesis of membrane proteins. To investigate molecular level lipid and additive interactions within the cubic phase, a method was developed for improving the resolution of (1)H NMR spectra when using a conventional solution state NMR probe. Using this approach we obtained well-resolved J-coupling multiplets in the one-dimensional NMR spectrum of the cubic-Ia3d phase prepared with hydrated monoolein. A high resolution t-ROESY two-dimensional (1)H NMR spectrum of the cubic-Ia3d phase is also reported. Using this new methodology, we have investigated the interaction of two additive molecules, L-tryptophan and ruthenium-tris(2,2-bipyridyl) dichloride (rubipy), with the cubic mesophase. Based on the measured chemical shift differences when changing from an aqueous solution to the cubic phase, we conclude that L-tryptophan experiences specific interactions with the bilayer interface, whereas rubipy remains in the aqueous channels and does not associate with the lipid bilayer.     

Spectral estimation of NMR relaxation

In this paper, spectral estimation of NMR relaxation is constructed as an extension of Fourier Transform (FT) theory as it is practiced in NMR or MRI, where multidimensional FT theory is used. nD NMR strives to separate overlapping resonances, so the treatment given here deals primarily with monoexponential decay. In the domain of real error, it is shown how optimal estimation based on prior knowledge can be derived. Assuming small Gaussian error, the estimation variance and bias are derived. Minimum bias and minimum variance are shown to be contradictory experimental design objectives. The analytical continuation of spectral estimation is constructed in an optimal manner. An important property of spectral estimation is that it is phase invariant. Hence, hypercomplex data storage is unnecessary. It is shown that, under reasonable assumptions, spectral estimation is unbiased in the context of complex error and its variance is reduced because the modulus of the whole signal is used. Because of phase invariance, the labor of phasing and any error due to imperfect phase can be avoided. A comparison of spectral estimation with nonlinear least squares (NLS) estimation is made analytically and with numerical examples. Compared to conventional sampling for NLS estimation, spectral estimation would typically provide estimation values of comparable precision in one-quarter to one-tenth of the spectrometer time when S/N is high. When S/N is low, the time saved can be used for signal averaging at the sampled points to give better precision. NLS typically provides one estimate at a time, whereas spectral estimation is inherently parallel. The frequency dimensions of conventional nD FT NMR may be denoted D₁, D₂, etc. As an extension of nD FT NMR, one can view spectral estimation of NMR relaxation as an extension into the zeroth dimension. In nD NMR, the information content of a spectrum can be extracted as a set of n-tuples (ω₁, … ω_n), corresponding to the peak maxima. Spectral estimation of NMR relaxation allows this information content to be extended to a set of (n + 1)-tuples (λ, ω₁, … ω_n), where λ is the relaxation rate.     

Sensitivity enhancement using paramagnetic relaxation in MAS solid-state NMR of perdeuterated proteins

Previously, Ishii et al., could show that chelated paramagnetic ions can be employed to significantly decrease the recycle delay of a MAS solid-state NMR experiment [N.P. Wickramasinghe, M. Kotecha, A. Samoson, J. Past, Y. Ishii, Sensitivity enhancement in C-13 solid-state NMR of protein microcrystals by use of paramagnetic metal ions for optimizing H-1 T-1 relaxation, J. Magn. Reson. 184 (2007) 350-356]. Application of the method is limited to very robust samples, for which sample stability is not compromised by RF induced heating. In addition, probe integrity might be perturbed in standard MAS PRE experiments due to the use of very short duty cycles. We show that these deleterious effects can be avoided if perdeuterated proteins are employed that have been re-crystallized from D(2)O:H(2)O=9:1 containing buffer solutions. The experiments are demonstrated using the SH3 domain of chicken alpha-spectrin as a model system. The labeling scheme allows to record proton detected (1)H, (15)N correlation spectra with very high resolution in the absence of heteronuclear dipolar decoupling. Cu-edta as a doping reagent yields a reduction of the recycle delay by up to a factor of 15. In particular, we find that the (1)H T(1) for the bulk H(N) magnetization is reduced from 4.4s to 0.3s if the Cu-edta concentration is increased from 0mM to 250 mM. Possible perturbations like chemical shift changes or line broadening due to the paramagnetic chelate complex are minimal. No degradation of our samples was observed in the course of the experiments.     

Towards rapid and unique curve resolution of low-field NMR relaxation data: trilinear SLICING versus two-dimensional curve fitting

In this work an alternative method, named SLICING, for two-dimensional and noniterative T(2) decomposition of low-field pulsed NMR data (LF-NMR) is proposed and examined. The method is based on the Direct Exponential Curve Resolution Algorithm (DECRA) proposed by W. Windig and A. Antalek (1997, Chemom. Intell. Lab. Syst.37, 241-254) and takes advantage of the fact that exponential decay functions, when translated in time, retain their characteristic relaxation times while only their relative amounts or concentrations change. By such simple translations (slicing) it is possible to create a new "pseudo" direction in the relaxation data and thus facilitate application of trilinear (multiway) data-analytical methods. For the application on LF-NMR relaxation data, the method has two basic requirements in practice: (1) two or more samples must be analyzed simultaneously and (2) all samples must contain the same qualities (i.e., identical sets of distinct T(2) values). In return, if these requirements are fulfilled, the SLICING (trilinear decomposition) method provides very fast and unique curve-resolution of multiexponential LF-NMR relaxation curves and, as a spin-off, calibrations to reference data referring to individual proton components require only scaling of the resulting unique concentrations. In this work the performance of the SLICING method (including multiple slicing schemes) is compared to a traditional two-dimensional curve fitting algorithm named MATRIXFIT through application to simulated data in a large-scale exhaustive experimental design and the results validated by application to two small real data sets. Finally a new algorithm, Principal Phase Correction (PPC) based on principal component analysis, is proposed for phase rotation of CPMG quadrature data, an important prerequisite to optimal SLICING analysis.     

Protein dynamics using frequency-dependent order parameters from analysis of NMR relaxation data

A novel approach is described to analyze NMR relaxation data on proteins. This method introduces the frequency-dependent order parameter, S(2)(omega), in order to estimate contributions to the generalized order parameter S(2) from different motional frequencies occurring on the picosecond to nanosecond time scales. S(2)(omega) is defined as the sum of a specified set of weighting coefficients from the Lorentzian expansion of the spectral density function. 15N NMR relaxation data (500, 600, and 800 MHz) on protein GB1 exemplify the method. Using this approach provides information on motional restrictions over specific frequency or time scale ranges and provides a normalized comparison of motional restrictions between proteins having different overall tumbling correlation times.     

Relationships between flow and NMR relaxation of fluids in porous solids.

Measurements are presented which correlate the displacements, X(Delta), determined by PGSE NMR, with the multi-mode transverse 1H NMR relaxation of water flowing through a glass bead pack, for which the dominant relaxation mechanism is diffusion through inhomogeneous internal magnetic fields. Analytical solution for the joint amplitude A[X(Delta), T(2k)] for the case of laminar flow in a circular pipe, with a diffusion-to-surface mechanism, shows that, for other than the lowest mode (k = 0), the contributions to the observed relaxation for a given X(Delta) may involve negative as well as positive amplitudes. The experimental measurements are shown to agree with this general conclusion, showing clear evidence of the presence of relaxation modes with negative amplitude at larger values of X(Delta). It is shown that in these, or similar measurements, which provide a spatially-resolved view of surface-mediated relaxation, allowance must be made for fitting with both positive and negative amplitudes.     

Orbital relaxation effects on temperature diagnostics of mid-Z plasmas

The orbital relaxation effect was studied in the calculations and diagnostics of the L-shell absorption spectra (2p→3d,4d,5d) of iron and bromine plasmas. A detailed level accounting model was developed to calculate the huge number of L-shell absorption lines of the two typical mid-Z plasmas. The orbital sets were generated by the optimizations according to the initial and final states, respectively. It was found that the L-shell line positions agree with the experimental iron and bromine spectra better when the orbital relaxations were included in calculations. Since experimental mid-Z spectra have few detailed line structures, calculations without considering orbital relaxations may misinterpret the spectra and consequently lead to underestimations of the plasma temperatures.     

Use of a modified DEFT pulse sequence in13C NMR: Dynamic range improvement for relaxation experiments and dynamic NMR measurements at high resolution

A modification of the DEFT pulse sequence is used for two applications in¹³C NMR spectroscopy. The first application suppresses solvent line resonances for dilute solutions. Unlike other techniques this method allows determination of solute T₁ values with concurrent solvent suppression. Requirements for this application are not overly stringent. The required T₁ ratio for effective peak suppression is ≿4; rf homogeneity must be moderately good. By contrast, the second application for this technique has very exacting requirements—in particular, very high rf homogeneity and accurate pulse timing. In this second application, the modified DEFT sequence is used to measure chemical exchange rates somewhat differently than in usual DNMR experiments. Results for amide bond rotation in N,N-dimethylacetamide are compared with literature values.     

NMR relaxation study of avocado quality

Four nuclear magnetic resonance relaxation protocols are investigated as potential candidates for off-line and on-line determination of avocado maturity. Two-dimensionalT ₁-T ₂ andT ₂-D correlation spectroscopy provides the most information but is only suitable for off-line quality control. The CPMGT ₂ spectrum gives avocado oil content but requires intensive data processing. Suppression of the tissue water signal byT ₁-Null methods is shown to be unreliable but a new, single-shot pulse sequence which uses diffusive attenuation to suppress the tissue water is shown to give a good correlation with oil content and is suitable for both off-line and on-line implementation.