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We use field-cycling-assisted dynamic nuclear polarization and continuous radio-frequency (RF) driving over a broad spectral range to demonstrate magnetic-field-dependent activation of nuclear spin transport from strongly hyperfine-coupled C13 sites in diamond. We interpret our observations with the help of a theoretical framework where nuclear spin interactions are mediated by electron spins. In particular, we build on the results from a four-spin toy model to show how otherwise localized nuclear spins must thermalize as they are brought in contact with a larger ancilla spin network. Further, by probing the system response to a variable driving field amplitude, we witness stark changes in the RF-absorption spectrum, which we interpret as partly due to contributions from heterogeneous multispin sets, whose zero-quantum transitions become RF active thanks to the hybrid electron-nuclear nature of the system. These findings could prove relevant in applications to dynamic nuclear polarization, spin-based quantum information processing, and nanoscale sensing.

Optical spin pumping of color centers in diamond is presently attracting broad interest as a platform for dynamic nuclear polarization at room temperature, but the mechanisms involved in the generation and transport of polarization within the host crystal are still partly understood. Here we investigate the impact of continuous radio-frequency (RF) excitation on the generation of nuclear magnetization produced by optical illumination. In the presence of RF excitation far removed from the nuclear Larmor frequency, we witness a magnetic-field-dependent sign reversal of the measured nuclear spin signal when the drive is sufficiently strong, a counterintuitive finding that immediately points to nontrivial spin dynamics. With the help of analytical and numerical modeling, we show our observations indicate a modified form of solid effect, down-converted from the microwave to the radio-frequency range through the driving of hybrid transitions involving one (or more) nuclei and two (or more) electron spins. Our results open intriguing opportunities for the manipulation of many-electron spin systems by exploiting hyperfine couplings as a means to access otherwise forbidden intraband transitions.

The Li + ion mobility through the porous cathode is a critical aspect in the development of commercial Li-air batteries. The bulk transport properties of lithium salts in organic solvents are not reliable parameters for the design of this type of battery since confinement could significantly modify the transport properties, especially when pore diameters are below 10 nm. In this work, we studied the effect of the carbon mesostructure and surface charge on the diffusion of LiTf and LiTFSI salts dissolved in diglyme, typical electrolytes for lithium-air batteries. Interdiffusion coefficients of the salts were determined using a conductimetric method. NMR spectroscopy and relaxometry were used to explore the effect of the carbon structure and the surface charge density on the interaction between the electrolytes and the pore wall. We showed that carbon micro/mesoporous structure plays a critical role in the transport properties of the electrolyte, producing a decrease of up to 2-3 orders of magnitude in the salt interdiffusion coefficients when going from bulk solutions to pores below 4 nm in diameter. It was observed that for pores 25 nm in diameter, the reduction in the diffusion coefficient can be mainly ascribed to the porosity of the sample, giving tortuosity factors around 1. However, for smaller pore sizes (1-10 nm diameter) bigger tortuosity coefficients were observed and were related to strong ion-pore wall interactions. Moreover, it was noticed that the ratio between the diffusion coefficients of the two studied salts dissolved in diglyme, is different in bulk and under confinement, demonstrating that the interactions of the ions with the charged pore wall probably compete with the cation-anion interactions, affecting salt association under confinement.

Multiphase aqueous-organic systems where a bicontinuous phase is in equilibrium with an excess organic and aqueous phase find various applications in industry. These systems─also known as Winsor III─are complex not only for the different phases that develop therein but also because they are multicomponent systems. In this work, we explore for the first time the use of a benchtop low-field single-sided NMR to determine the species distribution in Winsor III systems. The proposed methodology provides information at macroscopic and microscopic levels. In particular, we show the use of single-sided NMR to determine the phases' dimensions and the species distribution in a polymer-based bicontinuous system. The phases' dimensions and limits can be resolved with micrometric precision and are indicative of the bicontinuous phase stability. The species distribution is determined by means of spatially resolved NMR relaxation and diffusion experiments. It was observed that the salinity of the aqueous phase also impacts the species distribution in the bicontinuous system. Experiments show that the additive and the polymer are mainly located in the bicontinuous phase. As the salinity of the aqueous phase increases, the amount of organic components in the bicontinuous phase decreases as a consequence of the species distribution in the system. This influences the total amount of recovered organic liquid from the organic phase. The information is obtained in a relatively fast experiment and is relevant to the system's possible applications, such as enhanced oil recovery (EOR). This methodology is not only circumscribed to its application in EOR but can also be applied to the study of any emulsion or microemulsion systems without sample size or geometry constraints.

Among the many biopolymers that constitute food products, starch is one of the most common. Starch granules are often damaged in the milling process, which affects the final product quality, mainly due to changes in water adsorption properties. In this work, the crystallinity degree of wheat starch samples as a function of the mechanical damage is determined by low field 1 H NMR. We also introduce the use of single-sided NMR to determine granular swelling, water distribution and sorption dynamics of the samples. Results show that the crystallinity of the samples decreases with the milling. We also observed that swelling index and sorption capacity values are higher in the milled samples than in the native starch. Our experiments show how single-sided NMR is a valuable tool to provide information on dynamic processes not only in starch, but also in many carbohydrate polymeric samples with the additional benefit of spatial resolution., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Diffusion-relaxation correlation experiments in nuclear magnetic resonance are a powerful technique for the characterization of fluid dynamics in confined geometries or soft matter, in which relaxation may be either spin-spin (T 2 ) or spin-lattice (T 1 ). The general approach is to acquire a set of bidimensional data in which diffusion is codified by the evolution of the magnetization with either Hahn or stimulated echoes (STE) in the presence of a constant magnetic field gradient. While T 2 is codified by a Carr-Purcell-Meiboom-Gil (CPMG) sequence, T 1 is either encoded by saturation or inversion-recovery methods. In this work, we analyse the measurement time of diffusion-relaxation times in single-sided NMR and show that T 1 -D acquisition is always shorter than D-T 2 . Depending on the hardware characteristics, this time reduction can be up to an order of magnitude. We present analytical calculations and examples in model porous media saturated with water and in a dairy product., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The antiphase character of the PHIP associated signals after a hydrogenation reaction is particularly sensitive to line broadening introduced by magnetic field inhomogeneities and interferences by the presence of resonance lines steaming from a large amount of thermally polarized spins. These obstacles impose a limitation in the detection of reaction products as well as in the experimental setups. A simple way to overcome these impediments consists of acquiring the signal with a train of refocusing pulses instead of a single r.f. pulse. We present here a number of examples where this multipulse acquisition, denominated PhD-PHIP, displays its potentiality in improving the information related to hyperpolarized spins performed in a sample, where the former parahydrogen nuclei are part of a complex J-coupling network., (© 2021 Wiley-VCH GmbH.)

A new pulse sequence aimed to filter out NMR signals coming from thermally polarized protons in PHIP experiments based on the OPSY pulse sequence (Only Parahydrogen SpectroscopY) is presented. In analogy to OPSY, which removes thermal polarization by using a pair of magnetic field gradient pulses with an intensity ratio 1:2 and equal duration, the same effect can be achieved using inhomogeneous radiofrequency fields. The spatial dependence of the radiofrequency field is used to control the Hamiltonian, which results in an effective suppression of thermal contributions in the NMR signal, while PHIP originated signals remain unmodified. A theoretical model for the radiofrequency encoded only parahydrogen (REOPSY) sequence is presented along with an experimental implementation on a birdcage coil in a 7 T magnetic field. The control level achieved by this strategy allows the inclusion of a long train of refocusing pulses. Therefore, the new sequence can be combined with the parahydrogen discriminated PHIP (PhD-PHIP) pulse sequence as a detection block to improve sensitivity and resolution in a single-scan experiment. Experiments with REOPSY and REOPSY+PhD-PHIP are presented in thermally and hyperpolarized samples., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

DOSY is a powerful spectroscopic NMR technique that resolves components in mixtures through the evaluation of different diffusion coefficients. The application of DOSY to dilute mixtures is hampered by the low signal to noise ratios (SNR), leading to long acquisition times. The use of PHIP may resolve this issue as long as reproducible signals are obtained in order to perform 2D experiments. Here we show that the use of hollow membranes and adequate gas flow produce constant polarization for a time-span that enables the acquisition of 2D experiments. A pressure gradient is evidenced by the presence of convection, which is accounted for by using a DPGSE sequence. The influence of J-coupling evolution during the sequence is studied both numerically and experimentally, to determine the optimum echo-time. The applicability of the method for samples with poor SNR is explored by setting the reaction rate to achieve a low intensity of polarized signals., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Disorder and many body interactions are known to impact transport and thermalization in competing ways, with the dominance of one or the other giving rise to fundamentally different dynamical phases. Here we investigate the spin diffusion dynamics of 13 C in diamond, which we dynamically polarize at room temperature via optical spin pumping of engineered color centers. We focus on low-abundance, strongly hyperfine-coupled nuclei, whose role in the polarization transport we expose through the integrated impact of variable radio-frequency excitation on the observable bulk 13 C magnetic resonance signal. Unexpectedly, we find good thermal contact throughout the nuclear spin bath, virtually independent of the hyperfine coupling strength, which we attribute to effective carbon-carbon interactions mediated by the electronic spin ensemble. In particular, observations across the full range of hyperfine couplings indicate the nuclear spin diffusion constant takes values up to two orders of magnitude greater than that expected from homo-nuclear spin couplings., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

The ability of single-shot NMR imaging methods to follow the time evolution of a velocity distribution within an object is strongly limited by the phase errors accumulated as velocity maps are acquired. In the particular case of Carr-Purcell based sequences combined with Echo Planar Imaging acquisition, phase accumulates through subsequent images, hampering the possibility to acquire several velocity maps, which would be useful to determine transient behavior. In this work, we propose the use of a rewinding velocity encoding module applied after the acquisition of each image during the CPMG echo train. In this way, the first velocity module imparts a velocity dependent phase prior to the image acquisition and the second pair cancels this phase out before the next refocusing radiofrequency pulse is applied. The performance and limits of this method are studied by acquiring 100 images of a co-rotating Couette cell over a period of 1.6 s as a function of the rotation speed. The method is applied to determine the kinematic viscosity of a water/alcohol mixture, which is a relevant topic in many physical, chemical and biological processes., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Color-center-hosting semiconductors are emerging as promising source materials for low-field dynamic nuclear polarization (DNP) at or near room temperature, but hyperfine broadening, susceptibility to magnetic field heterogeneity, and nuclear spin relaxation induced by other paramagnetic defects set practical constraints difficult to circumvent. Here, we explore an alternate route to color-center-assisted DNP using nitrogen-vacancy (NV) centers in diamond coupled to substitutional nitrogen impurities, the so-called P1 centers. Working near the level anticrossing condition-where the P1 Zeeman splitting matches one of the NV spin transitions-we demonstrate efficient microwave-free 13 C DNP through the use of consecutive magnetic field sweeps and continuous optical excitation. The amplitude and sign of the polarization can be controlled by adjusting the low-to-high and high-to-low magnetic field sweep rates in each cycle so that one is much faster than the other. By comparing the 13 C DNP response for different crystal orientations, we show that the process is robust to magnetic field/NV misalignment, a feature that makes the present technique suitable to diamond powders and settings where the field is heterogeneous. Applications to shallow NVs could capitalize on the greater physical proximity between surface paramagnetic defects and outer nuclei to efficiently polarize target samples in contact with the diamond crystal., Competing Interests: The authors declare no conflict of interest.

Despite the large degree of polarization in PHIP experiments compared to the Boltzmann factor, the presence of a large amount of non-reacted molecules with thermal polarization is an important obstacle when dealing with very diluted samples. The feasibility of enhancing both sensitivity and resolution in a single experiment by combining two well established pulse sequences, OPSY and PHD-PHIP is presented. OPSY is used as a block for filtering the signals originated from thermally polarized protons. PhD-PHIP, on the other hand, is used as an acquisition block, increasing the resolution and further improving the sensitivity by preventing signal canceling in the presence of magnetic field inhomogeneities. Experiments in a complex sample with very low hyperpolarization levels are presented showing the excellent performance of the method., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Magnetic resonance imaging (MRI) has proven to be a powerful tool for the characterization and investigation of in situ chemical reactions. This is more relevant when dealing with complex systems, where the spatial distribution of the species, partition equilibrium, flow patterns, among other factors have a determining effect over mass transport and therefore over the reaction rate. The advantage of MRI is that it provides spatial information in a noninvasive way and does not require any molecular sensor or sample extraction. In this work, MRI is used to fully characterize an electrochemical reaction under forced hydrodynamic conditions. Reaction rates, flow patterns, and quantitative concentration of the chemical species involved are spatially monitored in situ in a complex system that involves metallic pieces and a heterogeneous cementation reaction. Experimental data are compared with numerical simulations., Competing Interests: The authors declare no competing financial interest.

We demonstrate that the relative phases in the refocusing pulses of multipulse sequences can compensate for pulse errors and off-resonant effects, which are commonly encountered in J-spectroscopy when CPMG is used for acquisition. The use of supercycles has been considered many times in the past, but always from the view point of time-domain NMR, that is, in an effort to lengthen the decay of the magnetization. Here we use simple spin-coupled systems, in which the quantum evolution of the system can be simulated and contrasted to experimental results. In order to explore fine details, we resort to partial J-spectroscopy, that is, to the acquisition of J-spectra of a defined multiplet, which is acquired with a suitable digital filter. We unambiguously show that when finite radiofrequency pulses are considered, the off-resonance effects on nearby multiplets affects the dynamics of the spins within the spectral window under acquisition. Moreover, the most robust phase cycling scheme for our setup consists of a 4-pulse cycle, with phases yyyy‾ or xxxx‾ for an excitation pulse with phase x. We show simulated and experimental results in both thermally polarized and PHIP hyperpolarized systems., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Two-dimension (2D) Nuclear Magnetic Resonance relaxometry experiments are a powerful tool extensively used to probe the interaction among different pore structures, mostly in inorganic systems. The analysis of the collected experimental data generally consists of a 2D numerical inversion of time-domain data where T 2 -T 2 maps are generated. Through the years, different algorithms for the numerical inversion have been proposed. In this paper, two different algorithms for numerical inversion are tested and compared under different conditions of exchange dynamics; the method based on Butler-Reeds-Dawson (BRD) algorithm and the fast-iterative shrinkage-thresholding algorithm (FISTA) method. By constructing a theoretical model, the algorithms were tested for a two- and three-site porous media, varying the exchange rates parameters, the pore sizes and the signal to noise ratio. In order to test the methods under realistic experimental conditions, a challenging organic system was chosen. The molecular exchange rates of water confined in hierarchical porous polymeric networks were obtained, for a two- and three-site porous media. Data processed with the BRD method was found to be accurate only under certain conditions of the exchange parameters, while data processed with the FISTA method is precise for all the studied parameters, except when SNR conditions are extreme., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The fluid dynamics of a liquid|liquid system inside a four-electrode electrochemical cell were studied by velocimetry magnetic resonance imaging (MRI) and flow propagator measurements. To characterize this system fully, three different cell configurations operating at two rotational frequencies were analyzed. Quantitative information about the stability of the liquid|liquid interface and the dynamics of the organic phase were determined. The NMR spectroscopy results were in agreement with the electrochemical measurements performed by using the same experimental setup., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In the present work we studied the catalytic activity of E. coli β-Gal confined in a nanoporous silicate matrix (E β-Gal ) at different times after the beginning of the sol-gel polymerization process. Enzyme kinetic experiments with two substrates (ONPG and PNPG) that differed in the rate-limiting steps of the reaction mechanism for their β-Gal-catalyzed hydrolysis, measurements of transverse relaxation times (T 2 ) of water protons through 1 H-NMR, and scanning electron microscopy analysis of the gel nanostructure, were performed. In conjunction, results provided evidence that water availability is crucial for the modulation observed in the catalytic activity of β-Gal as long as water participate in the rate limiting step of the reaction (only with ONPG). In this case, a biphasic rate vs. substrate concentration was obtained exhibiting one phase with catalytic rate constant (k cA ), similar to that observed in solution, and another phase with a higher and aging-dependent catalytic rate constant (k cB ). More structured water populations (lower T 2 ) correlates with higher catalytic rate constants (k cB ). The T 2 -k cB negative correlation observed along the aging of gels within the 15-days period assayed reinforces the coupling between water structure and the hydrolysis catalysis inside gels.

Hierarchical porous polymer systems are increasingly applied to catalysis, bioengineering, or separation technology because of the versatility provided by the connection of mesopores with percolating macroporous structures. Nuclear magnetic resonance (NMR) is a suitable technique for the study of such systems as it can detect signals stemming from the confined liquid and translate this information into pore size, molecular mobility, and liquid-surface interactions. We focus on the properties of water confined in macroporous polymers of ethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate [poly(EGDMA-co-HEMA)] with different amounts of cross-linkers, in which a substantial variation of hydroxyl groups is achieved. As soft polymer scaffolds may swell upon saturation with determined liquids, the use of NMR is particularly important as it measures the system in its operational state. This study combines different NMR techniques to obtain information on surface interactions of water with hydrophilic polymer chains. A transition from a surface-induced relaxation in which relaxivity depends on the pore size to a regime where the organic pore surface strongly restricts water diffusion is observed. Surface affinities are defined through the molecular residence times near the network surface.

Evaporation kinetics of water confined in hierarchal polymeric porous media is studied by low field nuclear magnetic resonance (NMR). Systems synthesized with various degrees of cross-linker density render networks with similar pore sizes but different response when soaked with water. Polymeric networks with low percentage of cross-linker can undergo swelling, which affects the porosity as well as the drying kinetics. The drying process is monitored macroscopically by single-sided NMR, with spatial resolution of 100 μm, while microscopic information is obtained by measurements of spin-spin relaxation times (T2). Transition from a funicular to a pendular regime, where hydraulic connectivity is lost and the capillary flow cannot compensate for the surface evaporation, can be observed from inspection of the water content in different sample layers. Relaxation measurements indicate that even when the larger pore structures are depleted of water, capillary flow occurs through smaller voids.

The effect of fiber addition on the distribution and mobility of protons in biscuits is studied by using low resolution time domain nuclear magnetic resonance (TD-NMR). The proportion of flour is reduced in order to incorporate inulin and oat fiber. NMR temperature dependent experiments are carried out in order to gain insight on the processes occurring in biscuit baking. Proton populations were identified measuring spin-spin relaxation times (T2). The major change in the relaxation profiles upon incorporation of fibers corresponds to mobile water molecules, which appear to be related to dough spreading behavior and biscuit quality. Biscuit samples baked in a commercial oven were studied by two dimensional spin-lattice/spin-spin (T1-T2) relaxation maps. The T1/T2 ratio is used as an indicator of the population mobility, where changes in the mobility of water in contact with flour components as starch, proteins and pentosans are observed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In the traditional view of temperature-driven volume phase transitions in PNIPAM-based microgel solutions, a monotonic and sharp decrease in the particle size occurs upon heating the solution to above the volume phase transition temperature (VPTT). However, at sufficiently high microgel concentrations and under low salt conditions, our dynamic light scattering experiments reveal an unexpected non-monotonic evolution of the particle size when increasing the solution temperature. These findings show that poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAM-co-MAA)) microgels swell upon heating the solution in the temperature range where NIPAM is water-soluble (i.e., below the VPPT). Further heating the microgel solution leads to microgel collapse as typically observed at temperatures above the VPTT. This novel behavior depends on the particle and salt concentration. We have observed the expected monotonic temperature-response of P(NIPAm-co-MAA) microgel solutions at low particle density and high salt concentration. To gain insights into the molecular origin of the unusual behavior of these microgel solutions, we have combined nuclear magnetic resonance studies and molecular-level theoretical calculations of the system. A delicate balance between inter-particle steric compressions and intra-microgel physical interactions and chemical equilibria determines the size of these microgels. Both steric compression, due to finite density, and hydrogen bond formation in the interior of the microgels favors a more compact particle. On the contrary, at the pH of the experiments the acid-base equilibrium constrains the polymer charge to increase, which favors particle swelling due to intra-microgel electrostatic repulsions. This interplay between physical interactions and chemical equilibria occurring at the nanometer length-scale determines the unusual thermal-induced swelling of P(NIPAM-co-MAA) microgels.

In this work we evaluate the performance of a 40-mm diameter bore 0.2T desktop Halbach tomograph to obtain 2D and 3D velocity maps for studying intra-aneurismal flow in the presence or absence of nitinol meshed implants with the aim of optimizing the flow diverter efficacy. Phantoms with known spatial velocity distribution were used to determine the performance of the MRI system. Maximum velocities of about 200mm/s could be measured with a precision of 1% at a spatial resolution of 0.5×0.5×1mm(3). This accuracy is suitable to evaluate in vitro intra-aneurismal flow under different conditions such as variable flow rates, different vessel-aneurysm geometry, as well as the influence of metallic flow diverters on the intra-aneurismal flow distribution. The information obtained non-invasively with desktop tomographs can be used to complement in vivo studies in order to decide the optimum flow diverter., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Parahydrogen induced polarization (PHIP) is a powerful hyperpolarization technique. However, as the signal created has an anti-phase characteristic, it is subject to signal cancellation when the experiment is carried out in inhomogeneous magnetic fields or in low fields that lack the necessary spectral resolution. The use of benchtop spectrometers and time domain (TD) analyzers has continuously grown in the last years and many applications are found in the food industry, for non-invasive compound detection or as a test bench for new contrast agents among others. In this type of NMR devices the combination of low and inhomogeneous magnetic fields renders the application of PHIP quite challenging. We have recently shown that the acquisition of J-spectra in high magnetic fields not only removes the anti-phase peak cancellation but also produces a separation of thermal from hyperpolarized signals, providing Parahydrogen Discriminated (PhD-PHIP) spectra. In this work we extend the use of PhD-PHIP to low and inhomogeneous fields. In this case the strong coupling found for the protons of the sample renders spin-echo spectra that have a great complexity, however, a central region in the spectrum with only hyperpolarized signal is clearly identified. This experimental approach is ideal for monitoring real time chemical reaction of pure PHIP signals., (Copyright © 2014 Elsevier Inc. All rights reserved.)

NMR is a fast, nondestructive, and noninvasive technique that can provide information about the pore structure of macroporous polymer beads and the dynamics of liquids confined in them. In this work, we describe the study of the pore structure of the macroporous polymer of ethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate [poly(EGDMA-co-HEMA)] in the dry but also in the swollen state by measuring relaxation times of liquids contained in the polymer network. The results show that the pore architecture differs from the dry to the soaked state. The behavior of polar liquids during evaporation and deswelling dynamics is monitored and described. An internal migration of water from the swollen polymer mesh into expanding pores takes place. With this procedure it is possible to obtain information about the microscopic morphology behavior of the matrix during evaporation and deswelling. This information is of great interest with the aspect of possible and future applications for these types of materials.

The application of parahydrogen for the generation of hyperpolarization has increased continuously during the last years. When the chemical reaction is carried out at the same field as the NMR experiment (PASADENA protocol) an antiphase signal is obtained, with a separation of the resonance lines of a few Hz. This imposes a stringent limit to the homogeneity of the magnetic field in order to avoid signal cancellation. In this work we detect the signal arising from hyperpolarized Hexene by means of a CPMG pulse train. After Fourier transformation the obtained J-spectra not only presents an enhanced spectral resolution but also avoids partial peak cancellation., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Nuclear spins are promising candidates for quantum information processing because their good isolation from the environment precludes the rapid loss of quantum coherence. Many strategies have been developed to further extend their decoherence times. Some of them make use of decoupling techniques based on the Carr-Purcell and Carr-Purcell-Meiboom-Gill pulse sequences. In many cases, when applied to inhomogeneous samples, they yield a magnetization decay much slower than that of the Hahn echo. However, we have proved that these decays cannot be associated with longer decoherence times, as coherences remain frozen. They result from coherences recovered after their storage as local polarization and thus they can be used as memories. We show here how this freezing of the coherent state, which can subsequently be recovered after times longer than the natural decoherence time of the system, can be generated in a controlled way with the use of field gradients. A similar behaviour of homogeneous samples in inhomogeneous fields is demonstrated. It is emphasized that the effects of inhomogeneities in solid-state nuclear magnetic resonance, independently of their origin, should not be disregarded, as they play a crucial role in multipulse sequences.

Two proton quasi-equilibrium states were previously observed in nematic liquid crystals, namely the S and W quasi-invariants. Even though the experimental evidence suggested that they originate in a partition of the spin dipolar energy into a strong and a weak part, respectively, from a theoretical viewpoint, the existence of an appropriate energy scale which allows such energy separation remains to be confirmed and a representation of the quasi-invariants is still to be given. We compare the dipolar NMR signals yielded both by the Jeener-Broekaert (JB) experiment as a function of the preparation time and the free evolution of the double quantum coherence (DQC) spectra excited from the S state, with numerical calculations carried out from first principles under different models for the dipolar quasi-invariants, in a 10-spin cluster which represents the 5CB (4(')-pentyl-4-biphenyl-carbonitrile) molecule. The calculated signals qualitatively agree with the experiments and the DQC spectra as a function of the single-quantum detection time are sensible enough to the different models to allow both to probe the physical nature of the initial dipolar-ordered state and to assign a subset of dipolar interactions to each constant of motion, which are compatible with the experiments. As a criterion for selecting a suitable quasi-equilibrium model of the 5CB molecule, we impose on the time evolution operator consistency with the occurrence of two dipolar quasi-invariants, that is, the calculated spectra must be unaffected by truncation of non-secular terms of the weaker dipolar energy. We find that defining the S quasi-invariant as the subset of the dipolar interactions of each proton with its two nearest neighbours yields a realistic characterization of the dipolar constants of motion in 5CB. We conclude that the proton-spin system of the 5CB molecule admits a partition of the dipolar energy into a bilinear strong and a multiple-spin weak contributions therefore providing two orthogonal constants of motion, which can be prepared and observed by means of the JB experiment. This feature, which implies the existence of two timescales of very different nature in the proton-spin dynamics, is ultimately dictated by the topology of the spin distribution in the dipole network and can be expected in other liquid crystals. Knowledge of the nature of the dipolar quasi-invariants will be useful in studies of dipolar-order relaxation, decoherence and multiple quantum NMR experiments where the initial state is a dipolar-ordered one.

Diffusion of atoms or molecules in presence of magnetic field gradients not only attenuates the NMR signal but also leads to distortions close to restricting boundaries. This phenomenon is most evident in imaging with laser polarized (LP) noble gases. Diffusion of gases can be manipulated, however, by admixing inert gases of different molecular weight. In this work we analyze the effect of mixing LP-(3)He with SF(6) on the image quality of a phantom consisting of an arrangement of capillaries with different diameters. Admixing buffer gases of higher molecular weight changes the contrast and offers a means to record images with high spatial and time resolution. Additionally we demonstrate how distortions due to edge enhancement can be reduced even for long timed MRI-sequences.

Previous work showed that by means of the Jeener-Broekaert (JB) experiment, two quasiequilibrium states can be selectively prepared in the proton spin system of thermotropic nematic liquid crystals (LCs) in a strong magnetic field. The similarity of the experimental results obtained in a variety of LC in a broad Larmor frequency range, with crystal hydrates, supports the assumption that also in LC the two spin reservoirs, into which the Zeeman order is transferred, originate in the dipolar energy and that they are associated with a separation in energy scales: A constant of motion related to the stronger dipolar interactions (S), and a second one (W) corresponding to the secular part of the weaker dipolar interactions with regard to the Zeeman and the strong dipolar part. We study the nature of these quasi-invariants in nematic 5CB (4(')-pentyl-4-biphenyl-carbonitrile) and measure their relaxation times by encoding the multiple-quantum coherences of the states following the JB pulse pair on two orthogonal bases, Z and X. The experiments were also performed in powder adamantane at 301 K which is used as a reference compound having only one dipolar quasi-invariant. We show that the evolution of the quantum states during the buildup of the quasiequilibrium state in 5CB prepared under the S condition is similar to the case of powder adamantane and that their quasiequilibrium density operators have the same tensor structure. In contrast, the second constant of motion, whose explicit operator form is not known, involves a richer composition of multiple-quantum coherences of even order on the X basis, in consistency with the truncation inherent in its definition. We exploited the exclusive presence of coherences of +/-4,+/-6,+/-8, besides 0 and +/-2 under the W condition to measure the spin-lattice relaxation time T(W) accurately, so avoiding experimental difficulties that usually impair dipolar order relaxation measurement such as Zeeman contamination at high fields and also superposition of the different quasi-invariants. This procedure opens the possibility of measuring the spin-lattice relaxation of a quasi-invariant independent of the Zeeman and S reservoirs, so incorporating a new relaxation parameter useful for studying the complex molecular dynamics in mesophases. In fact, we report the first measurement of T(W) in a LC at high magnetic fields. Comparison of the obtained value with the one corresponding to a lower field (16 MHz) points out that the relaxation of the W-order strongly depends on the intensity of the external magnetic field, similarly to the case of the S reservoir, indicating that the relaxation of the W-quasi-invariant is also governed by the cooperative molecular motions.

Distant dipolar fields among nuclear spins on macroscopic scales in the gas phase are reported for the first time. Their observation via interatomic multiple quantum coherences requires high nuclear spin polarization corresponding to spin temperatures of a few mK, which is generated in laser-polarized 3He, and proper control of the gas diffusion through a heavier buffer gas. This combination of physics at low and ambient temperatures opens up new ways of studying the relative translational diffusion of atoms and of gas diffusion in structures with a large range of length scales.

Spin echo formation in magnetic field gradients in the presence of fast stochastic motion is studied for hyperpolarized 3He gas at different diffusivities. The fast translational motion leads to frequency shifts already during echo formation, which can be described analytically for a linear gradient. Despite complete signal loss at the position of the spin echo itself, considerable intensity can be preserved at an earlier time (sqrt[2]tau rather than 2tau, where tau is the pulse delay). Hence, the phenomenon is designated as a pseudo spin echo.

Purpose: To study the influence of admixing inert buffer gases to laser-polarized (3)He in terms of resulting diffusion coefficients and the consequences for image contrast and resolution., Materials and Methods: The diffusion coefficient of (3)He was altered by admixing buffer gases of various molecular weights ((4)He, N(2), and SF(6)). The influence of the pulse sequence and the diffusion coefficient on the appearance of MRI of (laser-polarized) gases was analyzed by comparison of basic theoretical concepts with demonstrative experiments., Results: Excellent agreement between theoretical description and observed signal in simple gradient echoes was observed. A maximum signal gain can be predicted and was experimentally validated. Images acquired under such conditions revealed improved resolution. The nature and concentration of the admixed gas defines a structural threshold for the observed apparent diffusion coefficient (ADC) as demonstrated with diffusion-weighted MRI on a pig's lung flooded with suitable gas mixtures., Conclusion: A novel procedure is proposed to control the diffusion coefficient of gases in MRI by admixture of inert buffer gases. Their molecular mass and concentration enter as additional parameters into the equations that describe structural contrast. This allows for setting a structural threshold up to which structures contribute to the image. For MRI of the lung this enables images of very small structural elements (alveoli) only, or in the other extreme, all airways can be displayed with minimal signal loss due to diffusion., ((c) 2006 Wiley-Liss, Inc.)

The dependence of the individual mean square displacement of rare gases in binary mixtures is studied by a combined experimental and theoretical approach. We show that the diffusion constant can be varied in a considerable range by changing the molar fractions of the mixtures. On the experimental side, NMR diffusion measurements are done on hyperpolarized 3He and 129Xe, mixed with several inert buffer gases, in the presence of a magnetic field gradient. The results are compared to diffusion coefficients obtained from atomistic molecular dynamics simulations based on Lennard-Jones type potentials of the corresponding gas mixtures, and to appropriate analytical expressions, yielding very good mutual agreement. This study is the first quantitative validation of the effects of the mutual interactions between gas particles on the individual diffusion properties. It is shown that the dependency of gas phase diffusion properties on the local chemical environment may not be neglected, e.g. in diffusion-controlled chemical reactions.

We investigate the role that local motions and slow cooperative fluctuations have on the relaxation of the intrapair dipolar order in the nematic 5CB. With this purpose we present a theoretical and experimental systematic study which allow us to quantify the contribution from each type of molecular fluctuation to the intrapair dipolar order relaxation time, T(1D). The experimental work includes measurements of Zeeman and intrapair dipolar order relaxation times (T(1Z) and T(1D)) as a function of temperature at conventional NMR frequencies, in three complementary samples: normal and chain deuterated 4-n-pentyl-4(')-cyanobiphenyl (5CB and 5CB(d11)) and a mixture of normal 5CB and fully deuterated 4-n-pentyl-4'-cyanobiphenyl (5CB(d19)), 50% in weight. Additionally we perform T(1Z) field-cycling Larmor frequency-dependent measurements to obtain the spectral density of the cooperative fluctuations. The obtained results are as follows. (a) The cooperative molecular fluctuations have a strong relative weight in the relaxation of the intrapair dipolar order state, even at Larmor frequencies in the range of conventional NMR. (b) Alkyl chain rotations are an important relaxation mechanism of the intrapair dipolar order at megahertz frequencies. (c) Intermolecular fluctuations mediated by translational self-diffusion of the molecules is not an efficient mechanism of relaxation of the intrapair dipolar order.

With the use of hyperpolarized gases, a great number of experiments have been carried out in order to improve the diagnostics of the lung, both from a structural and a functional point of view. 3He is best suited for structural studies, whereas 129Xe gives more detailed information about the functionality of the lung because it enters the bloodstream. In this work, we propose the use of a gas mixture to perform consecutive analysis of lung structure and functionality upon the delivery of a single bolus of gas. We show images of a helium-xenon gas mixture in the presence of a small amount of liquid toluene in order to demonstrate how both nuclei can be detected independently, extracting the spectroscopic information provided by the 129Xe spectra and obtaining an image with high sensitivity for 3He. A second experiment performed on a dissected mouse lung was used to demonstrate how the mixture of gases can enhance sensitivity in the larger airways of the lung.

The procedures for the fixation of entire lungs of small rodents are presented together with various techniques used to verify the structural integrity of the lung tissue. To achieve this, the lungs were dissected out from rats and mice killed by ether overdose. The specimens were rinsed with isotonic saline and fixation solution under low vacuum conditions. After fixation, they were dried using alcohol and stored in a noncollapsed state (i.e., state of inhalation). Light and scanning electron microscopy as well as magnetic resonance imaging using hyperpolarized 3He were employed to verify the intact state on interalveolar septa and walls of smaller bronchi as well as accessibility of the air spaces.

Previous experiments of NMR spin-lattice relaxation times as a function of the Larmor frequency, as measured with the field-cycling technique (FC), were shown to be very useful to disentangle the various molecular motions, both local and collective, that dominate the relaxation in different time scales in liquid crystals. However, there are many examples where the known theoretical models that represent the molecular relaxation mechanisms cannot be fitted to the experimental trend in the region of low fields, making it difficult to obtain reliable values for the spectral densities involved, especially for the cooperative motions which dominate at low frequencies. In some cases, these anomalies are loosely ascribed to "local-field" effects but, to our knowledge, there is not a detailed explanation about the origin of these problems nor the range of frequencies where they should be expected. With the aim of isolating the dipolar effects from the influence of molecular dynamics, and taking into account the previous results in solids, in this work we investigate the response of the proton spin system of thermotropic liquid crystals 4-pentyl-4'-cyanobiphenyl (5CB) and 4-octyl-4'-cyanobiphenyl (8CB) in nematic and smectic A phases, due to the NMR multipulse sequence 90( composite function )y-(tau-thetax-tau)N. The nuclear magnetization presents an early transient period characterized by strong oscillations, after which a quasistationary state is attained. Subsequently, this state relaxes towards internal equilibrium over a time much longer than the transverse relaxation time T2. As occurs in solids, the decay time of the quasistationary state T2e presents a minimum when the pulse width thetax and the offset of the radiofrequency are set to satisfy resonance conditions (spin-lock). When measured as a function of the pulse spacing tau in "on-resonance" experiments, T2e shows the behavior expected for cross relaxation between the effective Zeeman and dipolar reservoirs, in accordance with the thermodynamic theory previously developed for solids. Particularly, for values of tau comparable with T2, the relaxation rate follows a power law T2e proportional to tau(-2), in all the observed cases, for the resonance conditions thetax=pi/3 and equivalent frequency omegae=pi/3tau. When tau is similar to or greater than typical dipolar periods, the relaxation rate becomes constant and for tau much shorter than T2, the thermodynamic reservoirs get decoupled. These experiments confirm that the thermodynamic picture is valid also in liquid crystals and the cross relaxation between the reservoirs can be detected without interference with spin-lattice relaxation effects. Accordingly, this technique can be used to estimate the frequency range, where cross-relaxation effects can be expected when Zeeman and dipolar reservoirs are put in thermal contact with each other and with the lattice, as in FC experiments. In particular, the present results allow us to associate the anomalies observed in low-field spin-lattice relaxation with nonadiabatic energy exchange between the reservoirs.

The NMR spin-lattice proton relaxation dispersion T1(nu(L)) of the liquid crystal propylcyano-phenylcyclohexane is studied over several decades of Larmor frequencies and at different temperatures in the nematic mesophase. The results show that the order fluctuation of the local nematic director contribution to T1(nu(L)) undergoes a transition between two power regimes: from T1(nu(L)) protional to nu(1/2)L to nu(alpha)L (alpha approximately 1/3) on going from low to high Larmor frequencies.

The NMR spin-lattice proton relaxation dispersion in the smectic mesophase of two liquid crystals, 4cyano-4'-8-alkylbiphenyl and 4,4'-bis-heptyloxyazoxybenzene, are studied over several decades of Larmor frequencies. The results show that the order fluctuation of the local smectic director contribution to T1(nu(L)) undergoes a transition between two power regimes: from T1(nu(L)) proportional, variantnu(1)(L) to nu(1/2)(L) on going from low to high Larmor frequencies. We explain this behavior by assuming, in the smectic mesophases, short coherence length nematiclike cooperative molecular reorientations.