Carr-Purcell-Meiboom-Gill Pulse Research Articles

Unravelling temperature-dependent molecular changes in hydrated wheat and maize starches using 1H time-domain NMR

This study proved that time-domain NMR (TD-NMR) experiments can accurately demonstrate the interaction between starch (wheat and maize) and water and the distribution of water molecules in starch-water systems during heating. Molecular properties in starch-water systems at 50% moisture content were monitored by Rhim and Kessemeier – Radiofrequency Optimized Solid-Echo (RK-ROSE) and Carr-Purcell-Meiboom-Gill (CPMG) pulse sequences at frequent (2 °C intervals) measurements during heating (55–80 °C). Starch-like and water-like phases were obtained by RK-ROSE and CPMG pulse sequences, respectively. The second moment, M2, along with the relaxation times of the populations, associated with fast-decaying protons, provided information on the crystal structure state during heating and the extent of gelatinisation. The relaxation times of the most abundant population from the CPMG signal decreased during heating due to strong interactions between starch and water. Temperature of stabilisation of this population aligned with the associated findings from the differential scanning calorimetry and rheological measurements.

Optimized Unilateral Magnetic Resonance Sensor with Constant Gradient and Its Applications in Composite Insulators

In this study, an optimized unilateral magnetic resonance sensor with a three-magnet array is presented for assessing the aging of composite insulators in power grids. The sensor’s optimization involved enhancing the static magnetic field strength and the homogeneity of the RF field while maintaining a constant gradient in the direction of the vertical sensor surface and maximizing homogeneity in the horizontal direction. The center layer of the target area was positioned 4 mm from the coil’s upper surface, resulting in a magnetic field strength of 139.74 mT at the center point of the area, with a gradient of 2.318 T/m and a corresponding hydrogen atomic nuclear magnetic resonance frequency of 5.95 MHz. The magnetic field uniformity over a 10 mm × 10 mm range on the plane was 0.75%. The sensor measured 120 mm × 130.5 mm × 76 mm and weighed 7.5 kg. Employing the optimized sensor, magnetic resonance assessment experiments were conducted on composite insulator samples utilizing the CPMG (Carr–Purcell–Meiboom–Gill) pulse sequence. The T2 distribution provided visualizations of the T2 decay in insulator samples with different degrees of aging.

CPMG pulse sequence for relaxation dispersion that cancels artifacts independently of spin states

The relaxation dispersion (rd) of nuclear magnetic resonance provides thermodynamic and kinetic information regarding molecules for which the conformations are exchanging in equilibrium. Experiments have often been implemented with Carr-Purcell-Meiboom-Gill (CPMG) pulse sequences for heteronuclear S-spin in SI and SI3 spin systems. One of the most common CPMG sequences contains a sequence called a P-element in the middle to average the different relaxation rates of anti-phase and in-phase coherences; however, its drawback is that the artifacts that can be compensated for are only those in one of the two S-spin doublet magnetization components, for example, SIα or SIβ in an SI spin system. Thus, when the CPMG sequence is followed by a normal heteronuclear single-quantum correlation (HSQC) sequence, the detected signal will also include the other component with accumulated artifacts. To overcome this issue, we developed a new pulse sequence (AFTAC) that can suppress artifacts in both the magnetization components. Its effectiveness was demonstrated by simulations and actual measurements targeting the methyl groups of dimethylsulfoxide and N, N-dimethyltrichloroacetamide. The results demonstrated that the AFTAC sequence sufficiently suppressed the artifacts, despite being followed by an HSQC sequence that detects both components. AFTAC is particularly suitable for the rd measurements of small molecules, which are usually not deuterated and are not subject to transverse relaxation optimized spectroscopy (TROSY) sequences. AFTAC does not require 1H continuous wave irradiation for I-spin decoupling, which is necessary for certain CPMG methods that maintain S-spin in-phase coherence during the CPMG period (Tcpmg). Therefore, AFTAC places less burden on the probe, even with a long Tcpmg. Furthermore, the AFTAC method achieves a similar artifact suppression quality not only in SI but also in SI2 and SI3 spin systems.

A methyl-TROSY based 13C relaxation dispersion NMR experiment for studies of chemical exchange in proteins.

A methyl Transverse Relaxation Optimized Spectroscopy (methyl-TROSY) based, multiple quantum (MQ) 13C Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion NMR experiment is described. The experiment is derived from the previously developed MQ 13C-1H CPMG scheme (Korzhnev in J Am Chem Soc 126: 3964-73, 2004) supplemented with a CPMG train of refocusing 1H pulses applied with constant frequency and synchronized with the 13C CPMG pulse train. The optimal 1H 'decoupling' scheme that minimizes the amount of fast-relaxing methyl MQ magnetization present during CPMG intervals, makes use of an XY-4 phase cycling of the refocusing composite 1H pulses. For small-to-medium sized proteins, the MQ 13C CPMG experiment has the advantage over its single quantum (SQ) 13C counterpart of significantly reducing intrinsic, exchange-free relaxation rates of methyl coherences. For high molecular weight proteins, the MQ 13C CPMG experiment eliminates complications in the interpretation of MQ 13C-1H CPMG relaxation dispersion profiles arising from contributions to exchange from differences in methyl 1H chemical shifts between ground and excited states. The MQ 13C CPMG experiment is tested on two protein systems: (1) a triple mutant of the Fyn SH3 domain that interconverts slowly on the chemical shift time scale between the major folded state and an excited state folding intermediate; and (2) the 82-kDa enzyme Malate Synthase G (MSG), where chemical exchange at individual Ile δ1 methyl positions occurs on a much faster time-scale.

Parallel transmission 2D RARE imaging at 7T with transmit field inhomogeneity mitigation and local SAR control

PurposeWe develop and test a parallel transmit (pTx) pulse design framework to mitigate transmit field inhomogeneity with control of local specific absorption rate (SAR) in 2D rapid acquisition with relaxation enhancement (RARE) imaging at 7T. MethodsWe design large flip angle RF pulses with explicit local SAR constraints by numerical simulation of the Bloch equations. Parallel computation and analytical expressions for the Jacobian and the Hessian matrices are employed to reduce pulse design time. The refocusing-excitation “spokes” pulse pairs are designed to satisfy the Carr-Purcell-Meiboom-Gill (CPMG) condition using a combined magnitude least squares-least squares approach. ResultsIn a simulated dataset, the proposed approach reduced peak local SAR by up to 56% for the same level of refocusing uniformity error and reduced refocusing uniformity error by up to 59% (from 32% to 7%) for the same level of peak local SAR compared to the circularly polarized birdcage mode of the pTx array. Using explicit local SAR constraints also reduced peak local SAR by up to 46% compared to an RF peak power constrained design. The excitation and refocusing uniformity error were reduced from 20%–33% to 4%–6% in single slice phantom experiments. Phantom experiments demonstrated good agreement between the simulated excitation and refocusing uniformity profiles and experimental image shading. ConclusionPTx-designed excitation and refocusing CPMG pulse pairs can mitigate transmit field inhomogeneity in the 2D RARE sequence. Moreover, local SAR can be decreased significantly using pTx, potentially leading to better slice coverage, enabling larger flip angles or faster imaging.

Observation of Arginine Side-Chain Motions Coupled to the Global Conformational Exchange Process in Deubiquitinase A

Coupled motions have been demonstrated to be functionally important in a number of enzymes. Noncovalent side-chain interactions play essential roles in coordinating the motions across different structural elements in a protein. However, most of the dynamic studies of proteins are focused on backbone amides or methyl groups in the side chains and little is known about the polar and charged side chains. We have previously characterized the conformational dynamics of deubiquitinase A (DUBA), an isopeptidase, on the microsecond-to-millisecond (μs–ms) time scales with the amide 1H Carr–Purcell–Meiboom–Gill (CPMG) experiment. We detected a global conformational exchange process on a time scale of approximately 200 μs, which involves most of the structural elements in DUBA, including the active site and the substrate binding interface. Here, we extend our previous study on backbone amides to the arginine side-chain Nε–Hε groups using a modified 1H CPMG pulse sequence that can efficiently detect both backbone amide and arginine side-chain Nε–Hε signals in a single experiment. We found that the side chains of three arginines display motions on the same time scale as the backbone amides. Mutations of two of the three arginines to alanines result in a decrease in enzyme activity. One of these two arginines is located in a loop involved in substrate binding. This loop is not visible in the backbone amide-detected experiments due to excess line broadening induced by motions on the μs–ms time scales. These results clearly demonstrate that the motions of some arginine side chains are coupled to the global conformational exchange process and provide an additional probe for motions in a functionally important loop that did not yield visible backbone amide signals, suggesting the value of side-chain experiments on DUBA. The modified 1H CPMG pulse sequence allows the simultaneous characterization of backbone and arginine side-chain dynamics without any increase in data acquisition time and can be applied to the dynamic studies of any protein that displays measurable amide 1H relaxation dispersion.

Reducing the effects of weak homonuclear dipolar coupling with CPMG pulse sequences for static and spinning solids

The Carr-Purcell/Meiboom-Gill (CPMG) pulse sequence, initially introduced for measuring transverse relaxation time constants (T2), can provide significant signal enhancements for solid-state NMR (SSNMR) spectra. The proper implementation of CPMG for acquiring spectra influenced by chemical shift anisotropies (CSAs), first and/or second order quadrupolar interactions, or paramagnetic broadening has been well documented to date, as have the effects of heteronuclear dipolar coupling on CPMG echo trains and T2 lifetimes. Homonuclear dipolar coupling can also impact T2 lifetimes and CPMG echo trains; these effects have been thoroughly investigated for spectra of homonuclear dipolar coupled spin-1/2 nuclei typically acquired under static conditions that are predominantly influenced by dipolar broadening (e.g., 1H, 19F, etc.). In particular, it has been shown that short refocusing pulses with small flip angles can extend the effective T2 (T2eff, the observed T2 constant as impacted by experimental conditions) measured by CPMG sequences for strong homonuclear dipolar coupled spin-1/2 pairs under static conditions. To date, these effects have not been explored for (i) spin-1/2 nuclei that have significant CSAs and simultaneously feature weak homonuclear dipolar couplings, (ii) for quadrupolar nuclei that are also weakly homonuclear dipolar coupled, and (iii) for either of these cases under magic-angle spinning (MAS) conditions. Herein, we demonstrate that short refocusing pulses that cause small flip angles can reduce the attenuation of signal in CPMG echo trains resulting from dipolar dephasing caused by the weak homonuclear dipolar couplings. For both spin-1/2 and quadrupolar nuclei, this can lead to significant extensions in T2eff and signal enhancements of up to three times compared to conventional CPMG in favourable cases. These phenomena can occur under both static and magic-angle spinning (MAS) conditions, in the latter of which homonuclear couplings are reintroduced by rotational resonance (R2) recoupling. Experimental examples of 13C (I = 1/2), 2H (I = 1), 87Rb (I = 3/2), 23Na (I = 3/2), and 35Cl (I = 3/2) NMR under static and MAS conditions, as well as simulations of these phenomena, are shown and discussed.

Volumetric and multispectral DWI near metallic implants using a non-linear phase Carr-Purcell-Meiboom-Gill diffusion preparation.

DWI near metal implants has not been widely explored due to substantial challenges associated with through-slice and in-plane distortions, the increased encoding requirement of different spectral bins, and limited SNR. There is no widely adopted clinical protocol for DWI near metal since the commonly used EPI trajectory fails completely due to distortion from extreme off-resonance ranging from 2 to 20 kHz. We present a sequence that achieves DWI near metal with moderate b-values (400-500 s/mm2 ) and volumetric coverage in clinically feasible scan times. Multispectral excitation with Cartesian sampling, view angle tilting, and kz phase encoding reduce in-plane and through-plane off-resonance artifacts, and Carr-Purcell-Meiboom-Gill (CPMG) spin-echo refocusing trains counteract T2* effects. The effect of random phase on the refocusing train is eliminated using a stimulated echo diffusion preparation. Root-flipped Shinnar-Le Roux refocusing pulses permits preparation of a high spectral bandwidth, which improves imaging times by reducing the number of excitations required to cover the desired spectral range. B1 sensitivity is reduced by using an excitation that satisfies the CPMG condition in the preparation. A method for ADC quantification insensitive to background gradients is presented. Non-linear phase refocusing pulses reduces the peak B1 by 46% which allows RF bandwidth to be doubled. Simulations and phantom experiments show that a non-linear phase CPMG pulse pair reduces B1 sensitivity. Application in vivo demonstrates complementary contrast to conventional multispectral acquisitions and improved visualization compared to DW-EPI. Volumetric and multispectral DW imaging near metal can be achieved with a 3D encoded sequence.

A multivariate approach to investigate the NMR CPMG pulse sequence for analysing low MW species in polymers.

Detection and quantification of low molecular weight components in polymeric samples via nuclear magnetic resonance (NMR) spectroscopy can be difficult due to overlapping signal caused by line broadening characteristics of polymers. A way of overcoming this problem could be the exploitation of the difference in relaxation between small molecules and macromolecular species, such as the application of a T2 filter by using the Carr-Purcell-Meiboom-Gill (CPMG) spin-echo pulse sequence. This technique, largely exploited in metabolomics studies, is applied here to material sciences. A Design of Experiments approach was used for evaluating the effect of different acquisition parameters (relaxation delay, echo time and number of cycles) and sample-related ones (concentration and polymer molecular weight) on selected responses, with a particular interest in performing a reliable quantitative analysis. Polymeric samples containing small molecules were analysed by NMR with and without the application of the filter, and analysis of variance was used to identify the most influential parameters. Results indicated that increasing the polymer concentration, hence sample viscosity, further attenuates polymer signals in CPMG experiments because the T2 of those signals tends to decrease with increasing viscosity. The signal-to-noise ratio measured for small molecules can undergo a minimum loss when specific parameters are chosen in relation to the polymer molecular weight. Furthermore, the difference in dynamics between aliphatic and aromatic nuclei, as well as between mobile and stiff polymers, translates into different results in terms of polymer signal reduction, suggesting that the relaxation filter can also be used for obtaining information on the polymer structure.

Proton spin relaxation study with pulsed NMR on the plasticization of Na+ ion-selective electrode membranes prepared from PVCs with different degrees of polymerization.

The proton spin-spin relaxation times (T2) of ion-selective electrode membranes with differences in the polymerization degree of the incorporated poly(vinyl chloride) (PVC) polymers were investigated. T2 measurements were performed using Hahn-Echo, Solid-Echo and Carr-Purcell-Meiboom-Gill (CPMG) pulse sequences. Analyses of the T2 measurements by Hahn-Echo pulse sequences could realize the estimation of the homogeneity and compatibility for a series of ion-selective electrode membranes and reveal a relationship with the electromotive force (EMF) response in the low-concentration region of the Na+ ions. On the other hand, the normalized derivative spectra from T2 measurements by Solid-Echo and CPMG pulse sequences could approximately visualize the degree of plasticization for such potentiometric polymeric membranes. Moreover, differences in the polymerization degrees of the incorporated PVCs were scarcely found to affect the selectivity coefficients of the Na+-ISEs based on bis(12-crown-4).

Optimized inside-out magnetic resonance probe for soil moisture measuring in situ.

We report a novel inside-out NMR (nuclear magnetic resonance) probe for the measurement of soil moisture. The probe consists of a dumbbell-shape magnet and an opposed-solenoid RF (radio frequency) coil. Optimization methods for the structure of the magnet and RF coil that maximize the SNR (signal-to-noise ratio) of NMR measurements are also described. The dumbbell-shape magnet consists of three cylindrical magnets in series whose magnetic field was calculated with analytic expression deduced by converting magnet to equivalent magnetization current on its cylindrical surface. Based on the analytic expression, a nonlinear optimization mathematical model was built to determine the optimal structure parameters automatically. The opposed-solenoid is a pair of reverse-connected solenoids and used as RF coil on inside-out NMR probe in this work. Its structure-parameter optimization was carried out based on FEM (finite element method) simulation, and UD (uniform design) was applied to increase the optimization efficiency. A prototype was designed and built consisting of a magnet with length of 100 mm and a diameter of 40 mm. An NMR-based soil moisture measuring experiment was conducted by this prototype, with NMR performed using the CPMG (Carr-Purcell-Meiboom-Gill) pulse sequence for soil sample in different moisture content. The T2 distribution spectrum reveals that there are two compartments of water in the soil sample: free water and bound water.

Анализ компонентного состава и свойств тяжёлых нефтей in situ методом ЯМР релаксации в низких магнитных полях

For the analysis of heavy oils, the method of simultaneous measurement of the free induction decay (FID) together with the decay of the echo signal in the Carr-Purcell-Meiboom-Gill (CPMG) pulse program was used. The measurements were carried out on a «Chromatek-Proton 20M» NMR analyzer operating at a frequency of 20 MHz. A special control program was created on the NMR analyzer that automatically tunes and measures the full FID curve, then switches to measuring the decay of the echo amplitude by the CPMG pulse sequence, and then the investigation ends with a joint processing of all the experimental data. This method makes it possible to measure the amplitudes of NMR signals and the relaxation times T2 of protons of heavy oil components in situ, including asphaltenes, without any perturbations in the analyzed system. Under the influence of paramagnetic centers located in asphaltenes, the amplitude-relaxation characteristics of oil protons are divided into 7 groups associated with solid asphaltenes in crystalline and amorphous states, resins with high and low density, aromatic and saturated compounds. The NMR amplitudes of these fractions correlate well with the group composition of heavy oils as determined by gravitational-chromatographic SARA method. The combined FID + CPMG method can be recommended for determining the SARA composition and other properties of oil in situ. The behavior of fractions of heavy oil in the temperature range (-15оС ÷ +60оС) was investigated by SARA-NMR method. For the first time in situ, it has been shown that resins participate in the formation of asphaltenes in a closed volume when the oil is cooled from a stable state at room temperature, and vice versa, asphaltenes are disaggregated by heating with the release of resins. The SARA-NMR method is promising for the on-line monitoring of the production, transportation and processing of heavy oil in real conditions of temperature, pressure and dissolved gases. However, the design of the NMR sensor must be adapted to industrial applications. The possibilities of designing NMR probes on process pipelines of larger diameter than in laboratory instruments can be extended taking into account the procedure proposed for correcting the inhomogeneity of the magnetic field in the probed volume based on the FID signal of the liquid oil fraction.

Characterization of the Initial Hydration Process of Ordinary Portland Cement Based on Low-Field NMR

Based on the advantages of nondestructive and noninvasive technique, high stability and continuity, currently, the low-field nuclear magnetic resonance (NMR) analyzing and testing technology (low-field NMR) has been used to characterize the initial hydration process of cement slurry system. As a kind of cement-based material, class G oil-well cement has been widely used in various cementing operations, and the basic research of class G oil-well cement has aroused wide attention. Simultaneously, microfine cement plays an increasingly important role as reinforcing material, especially in the cementing operation of low-temperature formation. Besides, the main advantage of Carr–Purcell–Meiboom–Gill (CPMG) technique with other spin echo techniques is that it allows rapid multiple accumulations of the echo train signal—an important issue in increasing the detection sensitivity at low fields. Therefore, during this study, the initial hydration process of class G oil-well cement and microfine cement was characterized by the values and distribution ranges of the time constants T2i [the attenuation of the function of the transverse magnetization 2 (t) was measured by means of CPMG pulse sequence, normalized to an initial value 2(0) = 1, and decomposed into a sum of exponential functions 2 (t) = Σ pi exp (− t/T2i) with the fractions Σ pi = 1]. As a result, it was confirmed that the low-field NMR has a great advantage in the characterization of early hydration reaction of cement-based material.

Analysis of Artifacts Caused by Pulse Imperfections in CPMG Pulse Trains in NMR Relaxation Dispersion Experiments

Nuclear magnetic resonance relaxation dispersion (rd) experiments provide kinetics and thermodynamics information of molecules undergoing conformational exchange. Rd experiments often use a Carr-Purcell-Meiboom-Gill (CPMG) pulse train equally separated by a spin-state selective inversion element (U-element). Even with measurement parameters carefully set, however, parts of 1H–15N correlations sometimes exhibit large artifacts that may hamper the subsequent analyses. We analyzed such artifacts with a combination of NMR measurements and simulation. We found that particularly the lowest CPMG frequency (νcpmg) can also introduce large artifacts into amide 1H–15N and aromatic 1H–13C correlations whose 15N/13C resonances are very close to the carrier frequencies. The simulation showed that the off-resonance effects and miscalibration of the CPMG π pulses generate artifact maxima at resonance offsets of even and odd multiples of νcpmg, respectively. We demonstrate that a method once introduced into the rd experiments for molecules having residual dipolar coupling significantly reduces artifacts. In the method the 15N/13C π pulse phase in the U-element is chosen between x and y. We show that the correctly adjusted sequence is tolerant to miscalibration of the CPMG π pulse power as large as ±10% for most amide 15N and aromatic 13C resonances of proteins.

General Expressions for Carr-Purcell-Meiboom-Gill Relaxation Dispersion for N-Site Chemical Exchange.

The Carr-Purcell-Meiboom-Gill (CPMG) nuclear magnetic resonance experiment is widely used to characterize chemical exchange phenomena in biological macromolecules. Theoretical expressions for the nuclear spin relaxation rate constant for two-site chemical exchange during CPMG pulse trains valid for all time scales are well-known as are descriptions of N-site exchange in the fast limit. We have obtained theoretical expressions for N-site exchange outside of the fast limit by using approximations to an average Liouvillian describing the decay of magnetization during a CPMG pulse train. We obtain general expressions for CPMG experiments for any N-site scheme and all experimentally accessible time scales. For sufficiently slow chemical exchange, we obtain closed-form expressions for the relaxation rate constant and a general characteristic polynomial for arbitrary kinetic schemes. Furthermore, we highlight features that qualitatively characterize CPMG curves obtained for various N-site kinetic topologies, quantitatively characterize CPMG curves obtained from systems in various N-site exchange situations, and test distinguishability of kinetic models.

Tuning the spin coherence time of Cu(II)-(bis)oxamato and Cu(II)-(bis)oxamidato complexes by advanced ESR pulse protocols.

We have investigated with the pulsed ESR technique at X- and Q-band frequencies the coherence and relaxation of Cu spins S = 1/2 in single crystals of diamagnetically diluted mononuclear [n-Bu4N]2[Cu(opba)] (1%) in the host lattice of [n-Bu4N]2[Ni(opba)] (99%, opba = o-phenylenebis(oxamato)) and of diamagnetically diluted mononuclear [n-Bu4N]2[Cu(opbon-Pr2)] (1%) in the host lattice of [n-Bu4N]2[Ni(opbon-Pr2)] (99%, opbon-Pr2 = o-phenylenebis(N(propyl)oxamidato)). For that we have measured the electron spin dephasing time Tm at different temperatures with the two-pulse primary echo and with the special Carr–Purcell–Meiboom–Gill (CPMG) multiple microwave pulse sequence. Application of the CPMG protocol has led to a substantial increase of the spin coherence lifetime in both complexes as compared to the primary echo results. It shows the efficiency of the suppression of the electron spin decoherence channel in the studied complexes arising due to spectral diffusion induced by a random modulation of the hyperfine interaction with the nuclear spins. We argue that this method can be used as a test for the relevance of the spectral diffusion for the electron spin decoherence. Our results have revealed a prominent role of the opba4– and opbon-Pr24– ligands for the dephasing of the Cu spins. The presence of additional 14N nuclei and protons in [Cu(opbon-Pr2)]2– as compared to [Cu(opba)]2– yields significantly shorter Tm times. Such a detrimental effect of the opbon-Pr24− ligands has to be considered when discussing a potential application of the Cu(II)−(bis)oxamato and Cu(II)−(bis)oxamidato complexes as building blocks of more complex molecular structures in prototype spintronic devices. Furthermore, in our work we propose an improved CPMG pulse protocol that enables elimination of unwanted echoes that inevitably appear in the case of inhomogeneously broadened ESR spectra due to the selective excitation of electron spins.

An adaptive method for determining an acquisition parameter t0 in a modified CPMG sequence

The modified CPMG (Carr-Purcell-Meiboom-Gill) pulse sequence is a common sequence used for measuring the internal magnetic field gradient distribution of formation rocks, for which t0 (the duration of the first window) is a key acquisition parameter. In order to obtain the optimal t0, an adaptive method is proposed in this paper. By studying the factors influencing discriminant factor σ and its variation trend using T2-G forward numerical simulation, it is found that the optimal t0 corresponds to the maximum value of σ. Then combining the constraint condition of SNR (Signal Noise Ratio) of spin echo, an optimal t0 in modified CPMG pulse sequence is determined. This method can reduce the difficulties of operating T2-G experiments. Finally, the adaptive method is verified by the results of the T2-G experiments for four water-saturated sandstone samples.

Finite pulse effects in CPMG pulse trains on paramagnetic materials.

The Carr-Purcell-Meiboom-Gill (CPMG) sequence is commonly used in high resolution NMR spectroscopy and in magnetic resonance imaging for the measurement of transverse relaxation in systems that are subject to diffusion in internal or external gradients and is superior to the Hahn echo measurement, which is more sensitive to diffusion effects. Similarly, it can potentially be used to study dynamic processes in electrode materials for lithium ion batteries. Here we compare the (7)Li signal decay curves obtained with the CPMG and Hahn echo sequences under static conditions (i.e., in the absence of magic angle spinning) in paramagnetic materials with varying transition metal ion concentrations. Our results indicate that under CPMG pulse trains the lifetime of the (7)Li signal is substantially extended and is correlated with the strength of the electron-nuclear interaction. Numerical simulations and analytical calculations using Floquet theory suggest that the combination of large interactions and a train of finite pulses, results in a spin locking effect which significantly slows the signal's decay. While these effects complicate the interpretation of CPMG-based investigations of diffusion and chemical exchange in paramagnetic materials, they may provide a useful approach to extend the signal's lifetime in these often fast relaxing systems, enabling the use of correlation experiments. Furthermore, these results highlight the importance of developing a deeper understanding of the effects of the large paramagnetic interactions during multiple pulse experiments in order to extend the experimental arsenal available for static and in situ NMR investigations of paramagnetic materials.

Detection of Iron Nanoparticles using Nuclear Magnetic Resonance Relaxometry and Inverse Laplace Transform

Department of Bioindustrial Machinery Engineering College of Agriculture and Life Sciences, Chonbuk National University, 567 Baekje-daero, Deokjin-gu, Jeonju-si 561-756, Republic of Korea Received: November 14th, 2014; Revised: November 24th, 2014; Accepted: November 26th, 2014 Purpose: Rapid detection of bacteria is very important in agricultural and food industries to prevent many foodborne illnesses. The objective of this study was to develop a portable nuclear magnetic resonance (NMR)-based system to detect foodborne pathogens (E. coli). This study was focused on developing a method to detect low concentrations of magnetic nanoparticles using NMR techniques. Methods: NMR relaxometry was performed to examine the NMR properties of iron nanoparticle mixtures with different concentrations by using a 1 T permanent magnet magnetic resonance imaging system. Exponential curve fitting (ECF) and inverse Laplace transform (ILT) methods were used to estimate the NMR relaxation time constants, T1 and T2, of guar gum solutions with different iron nanoparticle concentrations (0, 10-3, 10-4, 10-5, 10-6, and 10-7 M). Results: The ECF and ILT methods did not show much difference in these values. Analysis of the NMR relaxation data showed that the ILT method is comparable to the classical ECF method and is more sensitive to the presence of iron nanoparticles. This study also showed that the spin-spin relaxation time constants acquired by a Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence are more useful for determining the concentration of iron nanoparticle solutions comparwith the spin-lattice relaxation time constants acquired by an inversion recovery pulse sequence. Conclusions: We conclude that NMR relaxometry that utilizes CPMG pulse sequence and ILT analysis is more suitable for detecting foodborne pathogens bound to magnetic nanoparticles in agricultural and food products than using inversion recovery pulse sequence and ECF analysis.

Long-lived selective spin echoes in dipolar solids under periodic and aperiodicπ-pulse trains

The application of Carr-Purcell-Meiboom-Gill (CPMG) $\ensuremath{\pi}$ trains for dynamically decoupling a system from its environment has been extensively studied in a variety of physical systems. When applied to dipolar solids, recent experiments have demonstrated that CPMG pulse trains can generate long-lived spin echoes. In this work, we develop a theory to describe the spin dynamics in a dipolar coupled spin-$\frac{1}{2}$ system under a CPMG(${\ensuremath{\phi}}_{1},{\ensuremath{\phi}}_{2}$) pulse train, where ${\ensuremath{\phi}}_{1}$ and ${\ensuremath{\phi}}_{2}$ are the phases of the $\ensuremath{\pi}$ pulses. From our theoretical framework, the propagator for the CPMG(${\ensuremath{\phi}}_{1},{\ensuremath{\phi}}_{2}$) pulse train is equivalent to an effective ``pulsed'' spin locking of single-quantum coherences with phase $\ifmmode\pm\else\textpm\fi{}\frac{{\ensuremath{\phi}}_{2}\ensuremath{-}3{\ensuremath{\phi}}_{1}}{2}$, which generates a periodic quasiequilibrium that corresponds to the long-lived echoes. Numerical simulations, along with experiments on both magnetically dilute, random spin networks found in C${}_{60}$ and C${}_{70}$ and in nondilute spin systems found in adamantane and ferrocene, were performed and confirm the predictions from the proposed theory.