Fast Field Cycling NMR Relaxometry Research Articles

A New Model for Solving Hydrological Connectivity Inside Soils by Fast Field Cycling NMR Relaxometry

In this paper, a new quantitative approach for estimating the structural and functional connectivity inside soil by Fast Field Cycling (FFC) NMR relaxometry is presented, tested by measurements carried out in three samples with different texture characteristics. Measurements by FFC NMR relaxometry have been carried out using water-suspended samples and Proton Larmor frequencies (νL) ranging in the 0.015–35 MHz interval. Two non-degraded soil samples, with different textural characteristics, and a degraded soil collected in a badland area, were analyzed. For a given soil and any applied Proton Larmor frequency, the distribution of the longitudinal relaxation times, T1, (i.e., relaxogram) measured by FFC NMR has been integrated, and the resulting S-shaped curve (i.e., relaxogram integration curve) was represented, for the first time, by Gumbel’s diagram. This new representation of the relaxogram integration curve, transforming the S-shaped curve into a straight line, allowed for distinguishing three linear components, corresponding to three different relaxation time ranges, characterized by three different slopes. Two points, identified by the abrupt slope changes of the relaxogram integration curve plotted in Gumbel’s diagram, are used to identify two characteristic values of relaxation time, T1A and T1B, which define three well-known pore size classes (T1 < T1A micro-pores, T1A < T1 < T1B meso-pores, and T1 > T1B macro-pores). The relaxogram integration curve allowed for calculating the non-exceeding empirical cumulative frequency, F(T1), corresponding to the characteristic T1A and T1B values. The analysis demonstrated that the relaxogram can be used to determine the pore-size ranges of each investigated sample. Finally, using the slope values of the three components of the relaxogram integration curve, a new definition of the Structural Connectivity Index, SCI, and Functional Connectivity Index, FCI, was proposed.

Physicochemical characterization of green sodium oleate-based formulations. Part 3. Molecular and collective dynamics in rodlike and wormlike micelles by proton nuclear magnetic resonance relaxation

HypothesisSodium oleate (NaOL) self-aggregates in water forming rodlike micelles with different length depending on NaOL concentration; when KCl is added wormlike micelles form, which entangle giving rise to a viscoelastic dispersion. It is expected that aggregates with different size and shape exhibit different internal and overall molecular motions and collective dynamics. ExperimentsTwo low viscosity NaOL/water and two viscoelastic NaOL/KCl/water formulations with different NaOL concentration (0.23 and 0.43 M) were investigated by 1H fast field cycling NMR relaxometry over broad temperature and Larmor frequency ranges, after a first screening by 1H and 13C NMR spectroscopy at high frequency. FindingsThe analysis of the collected data indicated that fast conformational isomerization and rotation of NaOL about its long molecular axis and lateral diffusion of NaOL around the axis of the cylindrical aggregates are slightly affected by the aggregate shape and length. On the other hand, fluctuations of the local order director are quite different in the fluid and viscoelastic systems, reflecting the shape and size of the aggregates. Quantitative information was obtained on activation energy for fast internal and overall motions, correlation times and activation energy for lateral diffusion, and coherence length for collective order fluctuations.

Use of magic sandwich echo and fast field cycling NMR relaxometry on honey adulteration with corn syrup

Adulteration is defined as the intentional addition of a material that is not a part of the nature. In this study, a non-conventional time domain nuclear magnetic resonance (TD-NMR) pulse sequence: magic sandwich echo (MSE) was used to detect the adulteration of honey by glucose syrup (GS) and high fructose corn syrup (HFCS) accompanied with T1 and T2 relaxation times. Also, fast field cycling NMR (FFC-NMR) relaxometry and multivariate analysis were performed to investigate the adulteration. Higher maltose in GS and changing glucose to water ratio of HFCS gave high correlation with the crystal content values. In HFCS adulteration, two separate populations of protons having different T2 values were detected and T1 times were also used to determine GS adulteration. Addition of GS increased T1 while addition of HFCS increased T2 , significantly. The results showed that it is possible to differentiate the unadulterated and adulterated honey samples by using TD-NMR relaxation times and crystal content values obtained by the MSE sequence. By FFC-NMR relaxometry, not only GS addition but also the amount of GS was examined. The multivariate analysis technique of principal component analysis was able to distinguish the types of adulterants. © 2021 Society of Chemical Industry.

Rotational correlation times, diffusion coefficients and quadrupolar peaks of the protic ionic liquid ethylammonium nitrate by means of 1H fast field cycling NMR relaxometry

The protic ionic liquid (PIL) ethylammonium nitrate (EAN) is characterized by hydrogen bonding between the NH bonds of the cations and the oxygen atoms of the anions. The three-dimensional H-bond network of EAN very much resembles that of water. Although this first ionic liquid is known for more than 100 years, there is still lack of information about the rotational and translational dynamics, and how both are related to each other. For that purpose, we measured the 1H nuclear magnetic relaxation dispersion curves (NMRD) of EAN by means of Fast Field Cycling (FFC) NMR relaxometry. We were able to analyze the measured 1H spin-lattice relaxation rates R1 covering a large temperature range between 248 and 333 K simultaneously. Applying the well-known Bloembergen-Purcell-Pound (BPP) approach, we decomposed the total relaxation rates into intramolecular and intermolecular contributions, describing the rotational and translational dynamics of the ethylammonium cation. Here, we report rotational correlation times, τR, and translational diffusion coefficients, DT, both derived from the total 1H spin-lattice relaxation rates as a function of temperature and frequency. Self-diffusion coefficients, DT, were also determined from the total relaxation rates in the low frequency range, wherein only the intermolecular relaxation contribution is frequency dependent. Then, DT results from the slope of a linear fit of the spin-lattice relaxation rate R1 as a function of the square root of frequency, ν. The diffusion coefficients obtained from both methods are in good agreement with self-diffusion coefficients measured by pulsed-field-gradient (PFG) NMR. The rotational correlation times, τR, derived from the intramolecular 1H relaxation contribution were compared to correlation times obtained from high-field NMR deuteron relaxation experiments, dielectric spectroscopy (DS) and femto-second-infrared (fs-IR) spectroscopy. For EAN, we also observed a local enhancement of the 1H spin-lattice relaxation rates R1 at high frequencies. This so-called quadrupole relaxation enhancement (QRE) results from the interference of the Zeeman transition energy of the 1H spins and the energy difference of two levels of the quadrupole 14N nuclei. QRE is usually known for solids, but rarely for the liquid state as observed here for EAN. Overall, we show that FFC relaxometry provides access to rotational correlation times, translational diffusion coefficients and quadrupole relaxation enhancement at the same time.

Fast field cycling NMR relaxometry as a tool to monitor Parmigiano Reggiano cheese ripening

It is widely recognized that the longer the ageing, the more valuable Parmigiano Reggiano (PR) cheese becomes, due to the improvement of its sensorial and nutritional properties. Up to now, the evaluation of PR properties has been performed on samples mainly aged up to 40 months. For this reason, this study was aimed at collecting information about the chemical-physical characteristics of PR cheeses after ageing at 24, 48 and 84 months. The basic analyses on water amount, protein content and volatile organic compounds (VOC) revealed that PR ageing is associated to the decomposition of the organic components into smaller units. This drives water molecules closer to the aforementioned units, thereby leading to a reduction of water activity. Moreover, it appears, from VOC investigation, that either the total amount of long chain fatty acids (LCFA) or the sole 9Z-octadecenoic acid considerably increased with PR aging, thereby making these molecular systems good fingerprint to monitor PR ripening. Fast field cycling (FFC) NMR relaxometry revealed different components of the molecular dynamics in the complex PR cheese samples, which were attributed to water trapped in casein micelles, water bound to polar groups in organic components, proteins, and fats. In particular, the reduction of the correlation times associated to the organic components was explained by the molecular size decrement following degradation processes. The ageing-independent component of the motion was assigned to water molecules bound to polar groups in organic moieties. Finally, the ageing-independent contribution to the overall relaxation rate was assigned to water molecules in casein micelles. This study revealed that FFC NMR relaxometry can be a promising technique to monitor the chemical physical changes during Parmigiano Reggiano cheese ripening.

Use of 1H-NMR spectroscopy, diffusometry and relaxometry for the characterization of thermally-induced degradation of motor oils

We explore the capability of 1H NMR spectroscopy, relaxation and diffusion for the characterization of thermally-induced degradation of fresh motor oils. Temperature dependent measurements of diffusion show a weak sensitivity to thermal degradation. In contrast, both the transverse relaxation at 1H Larmor frequencies of 20 MHz and 400 MHz, as well as the longitudinal relaxation at 60 kHz showed to be sensitive to thermally-induced effects at measured temperatures within the range −10 °C to 30 °C. Results show that the highest sensitivity significance can be reached by fast field-cycling NMR relaxometry measurements at low magnetic fields.

Quantification of manganous ions in wine by NMR relaxometry

Proton relaxation in model and real wines is investigated for the first time by fast field cycling NMR relaxometry. The relaxation mechanism unambiguously originates form proton interaction with paramagnetic ions naturally present in wines. Profiles of a white Chardonnay wine from Burgundy, a red Medoc, and model wines are well reproduced by Solomon-Bloembergen-Morgan equations. Relaxation is primarily governed by interactions with Mn2+. A straightforward model-independent quantification of the manganese ion concentration (down to few tens of μg/L) is proposed.

Comparing different processing methods in apple slice drying. Part 2 solid-state Fast Field Cycling 1H-NMR relaxation properties, shrinkage and changes in volatile compounds

The objective of this paper was to study the effects of three different drying methods: microwave (MW), hot air (HA) and a combination of both (HY), on the 1H NMR relaxation properties, shrinkage and volatile compounds of Golden Delicious apple slices. Fast field cycling NMR relaxometry revealed that the HA samples dried at different temperatures (65 and 75 °C) appeared to contain less restrained water as compared to the sample obtained by MW heating at the same temperatures. In fact, the longitudinal relaxation times (T1) of the water molecules in the HA dried slices were shorter than those measured for the MW dried samples, thereby revealing that in the MW slices, water molecules behave more like as a pseudo-ice layer. For this reason, shrinkage was much more accentuated in apples dried by the HA and hybrid methods, compared to the MW procedure. Likewise, HA drying had a bigger effect than MW and HY on the aromatic profile of the apple slices, causing a significant decrease in esters while ketones increased.

Standardizing the use of fast-field cycling NMR relaxometry for measuring hydrological connectivity inside the soil.

Hydrological connectivity inside the soil (HCS) is applied to study the effects of heterogeneities in complex environmental systems. It refers to both the spatial patterns inside the soil (i.e., structural connectivity [SC]) and the physical-chemical processes at a molecular level (i.e., functional connectivity [FC]). NMR relaxometry has been already applied to assess both SC and FC components of the HCS by defining SC and FC indexes. Here, fast-field cycling NMR relaxometry has been applied on a water suspended soil and a sediment to optimize the conditions to standardize the technique. Proton Larmor frequencies (ωL ) from 0.01 to 25MHz were used on samples suspended in three different rates of Milli-Q grade water. The application of different magnetic fields revealed that the T1 values of the sediment sample are always shorter than those measured for the soil sample. This difference was attributed to the soil erosion processes limiting FC by reducing the size of macropores. For the soil sample, analyses showed that both structural and functional connectivity indexes can be assumed ωL independent. For the sediment sample, the connectivity indexes resulted ωL independent only for ωL ≥0.1MHz. This could be due either to instrumental problems for ωL <0.1MHz or to a real magnetic field effect when a finer textured sample is examined. Further research is required in this area. Finally, the experiments revealed that the optimal water amount to obtain reliable results was corresponding to the water holding capacity.

Trapping of Gd(III) Ions by Keplerate Polyanionic Nanocapsules in Water: A 1H Fast Field Cycling NMR Relaxometry Study

Polyoxomolybdates of the type [{MoVIMoVI5O21(H2O)6}12{MoV2O4(L)}30](12+30n)–, also referred to as keplerates (Kps), are polyanionic nanocapsules bearing 20 {Mo9O9} pores connected to a central cavity by 20 channels. In solution, they can entrap cations in different sites of their porous structure (in the internal cavity, in the pores, or on the capsule surface) in equilibrium with cations free in solution. The porosity of Kps was previously exploited to prepare nanostructured potential contrast agents through the self-assembly of KpOAc or KpHPO4 (i.e., Kp with L = acetate or hydrogen phosphate) macroanions and Gd(III) cations in water, accompanied by stabilization with F-127 Pluronics. The strongly enhanced water proton relaxivity observed at 20 MHz was postulated to derive from the trapping of Gd(III) aqua ions by the nanocapsules. In the present work, 1H fast field cycling NMR relaxometry allowed this hypothesis to be verified on aqueous suspensions containing either KpOAc or KpHPO4 and Gd(III) in diffe...

Exploring the tumour extracellular matrix by in vivo Fast Field Cycling relaxometry after the administration of a Gadolinium-based MRI contrast agent.

1 H Fast Field Cycling NMR (FFC-NMR) relaxometry is proposed as a powerful method to investigate tumour stroma in vivo upon the administration of a Gd-based contrast agent. To perform this study, an FFC-NMR equipment endowed with a wide bore magnet was used for the acquisition of Nuclear Magnetic Resonance Dispersion profiles on healthy muscle and tumour tissue in living mice. At magnetic field strengths < of ca. 1MHz, the differences in the relaxation rates of the intra and extracellular compartment become of the same order of magnitude of the exchange rate across the cellular membranes. Under this condition, the water exchange rate between the two compartments yields to a biexponential magnetization recovery that can be analysed by fitting the experimental data with the two-Site eXchange (2SX) model. Using this model, it was possible to obtain, for the two compartments, both relaxation properties and water kinetic constants for water exchange across cell membranes. The method allowed us to determine the effect of the "matrix" on the water proton relaxation times and, in turn, to get some insights of the composition of this compartment, till now, largely unknown.

Relaxometric investigations addressing the determination of intracellular water lifetime: a novel tumour biomarker of general applicability

ABSTRACT1H Fast-Field Cycling NMR relaxometry is proposed as a powerful method to investigate tumour cell metabolism by measuring changes in cell water content and mobility across the cellular membrane. Measurements of intracellular water residence time in cultured cells were carried out by measuring T1 at fixed field (0.2 T) after the addition of a paramagnetic Gd complex (Prohance) at different concentrations in the external medium. Investigations on tumour cells (mammary adenocarcinoma TS/A) grown in normo- or hypoxic conditions or suspended in ‘hypo-osmotic’ solutions allowed us to demonstrate that both hypoxic and hypo-osmotic conditions cause a marked increase in water mobility as assessed by the elongation of T1. Conversely, the metabolic change caused by glutamine (an aminoacid essential for tumour growth) deprivation caused a water mobility decrease (shorter T1). These findings suggest that T1 measurements at low and variable magnetic field strengths, giving access to the assessment of intracellular water lifetime, can provide important information about tumour cell metabolism in real time and non-invasively.

Rouse dynamics in PEO-PPO-PEO block-copolymers in aqueous solution as observed through fast field-cycling NMR relaxometry

We present a proton fast field-cycling (FFC) NMR relaxometry study of the molecular dynamics in three different deuterated water-dispersed triblock copolymers of ethylene oxide (EO) and propylene oxide (PO):EO80PO27EO80(F68), EO141PO44EO141 (F108), and EO101PO56EO101(F127). Independently of the phase and molecular arrangement, bi-exponential decays of the magnetization during the spin-lattice relaxation process could be observed for F127, while mono-exponential decays were measured for F68 and F108. This fact has been attributed to the relative ratio of PEO and PPO protons for each case. In F127, each component of the magnetization decay could be associated with a particular block of the co-polymer. A direct consequence of this fact is the independent characterization of the molecular dynamics of each block. It was found that the dominant relaxation mechanism can be attributed to the Rouse model, and it seems to be independent on whether the molecules are incorporated into a micelle, or as individual unimers in the aqueous solution. The experimental results and the provided explanation are consistent with entanglement-free self-assembled structures, and a fast exchange of unimers between the micellar structure and the solvent. This particular feature was also investigated in F68 and F108, although for these cases a mono-exponential decay of the magnetization was observed. NMR relaxometry results are complemented with other relaxation experiments in the rotating frame, NMR spectroscopy and atomic-force microscopy.

Hydration of MgO-Based Cement: Water Dynamics by 1H Fast Field-Cycling NMR Relaxometry

1H Fast Field-Cycling (FFC) NMR relaxometry was applied for the first time to monitor the state of water during the hydration reaction of MgO and silica that brings to the formation of magnesium silicate hydrate (M-S-H), the binder phase of innovative cements with promising applications in the containment of radioactive waste. To this aim water proton longitudinal relaxation rates (R1=1/T1) were measured in the Larmor frequency range between 10 kHz and 30 MHz at different hydration times ranging from 0.5 h to ~ 4 months. The obtained R1 vs frequency (NMRD) curves were analyzed considering fast exchange of water molecules between a hydration layer, where dynamics is affected by interactions with the surface of solids present in the reacting mixture, and a bulk phase. For the hydration layer, water molecules undergoing fast local molecular dynamics on the surface gave a constant contribution to R1 throughout the investigated frequency range; on the other hand, water molecules undergoing slow dynamics on the...

Correction of environmental magnetic fields for the acquisition of Nuclear magnetic relaxation dispersion profiles below Earth’s field

T1 relaxation times can be measured at a range of magnetic field strengths by Fast Field-Cycling (FFC) NMR relaxometry to provide T1-dispersion curves. These are valuable tools for the investigation of material properties as they provide information about molecular dynamics non-invasively. However, accessing information at fields below 230 μT (10kHz proton Larmor frequency) requires careful correction of unwanted environmental magnetic fields.In this work a novel method is proposed that compensates for the environmental fields on a FFC-NMR relaxometer and extends the acquisition of Nuclear Magnetic Relaxation Dispersion profiles to 2.3μT (extremely low field region), with direct application in the study of slow molecular motions. Our method is an improvement of an existing technique, reported by Anoardo and Ferrante in 2003, which exploits the non-adiabatic behaviour of the magnetisation in rapidly-varying magnetic fields and makes use of the oscillation of the signal amplitude to estimate the field strength. This increases the accuracy in measuring the environmental fields and allows predicting the optimal correction values by applying simple equations to fit the data acquired. Validation of the method is performed by comparisons with well-known dispersion curves obtained from polymers and benzene.

Dynamical regimes of lipids in additivated liposomes with enhanced elasticity: A field-cycling NMR relaxometry approach

We study the molecular dynamics of lipids in binary large unilamellar liposomes suspended in D2O composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) or soy phosphatidylcholine (SPC) additivated with different percentiles of sodium deoxycholate (SDC). We use the fast field-cycling proton NMR relaxometry technique over a wide timescale and at diverse temperatures. A model previously validated in different formulations is here employed for the relaxometric analysis of elastic vesicles. A new dynamical regime is observed for the first time in additivated DMPC and additivated/non-additivated SPC liposomes. This surprising feature is discussed in terms of vesicle shape fluctuations, enhanced elasticity and lipid & additive diffusion within the membrane. The continuum elastic theory is revisited for a better understanding of recent experiments and those here presented. We address the point of deformability measurements across rigid permeable barriers versus measurements of the bending elastic modulus in free-standing vesicles.

Dynamics of poly(vinyl butyral) studied using dielectric spectroscopy and 1H NMR relaxometry.

Dielectric Spectroscopy (DS) and 1H Fast Field-Cycling (FFC) NMR relaxometry were applied for understanding the dynamic behavior of the amorphous ter-polymer poly(vinyl butyral) (PVB) across the glass transition temperature (Tg = 70 °C by Differential Scanning Calorimetry). Above Tg, main chain segmental motions (α relaxation) were detected and characterized using both DS and FFC NMR relaxometry. The correlation times extracted by the analysis of DS and FFC NMR relaxometry data agreed within a factor of three and showed a Vogel-Fulcher-Tammann temperature dependence, with an associated Tg of 69 °C and a fragility of 155 for PVB glass. Below Tg, a secondary process (β relaxation) was revealed by DS, and was ascribed to reorientations of the vinyl alcohol dipoles due to local twisting motions with an associated activation barrier of 11 kcal mol-1. The β process was also found to contribute to 1H NMR relaxation above Tg.

Measurement of the bending elastic modulus in unilamellar vesicles membranes by fast field cycling NMR relaxometry

The elastic properties of lipid membranes can be conveniently characterized through the bending elastic modulus κ. Elasticity directly affects the deformability of a membrane, morphological and shape transitions, fusion, lipid-protein interactions, etc. It is also a critical property for the formulation of ultradeformable liposomes, and of interest for the design of theranostic liposomes for efficient drug delivery systems and/or different imaging contrast agents. Measurements of κ in liposome membranes have been made using the fast field cycling nuclear magnetic relaxometry technique. We analyze the capability of the technique to provide a consistent value of the measured quantity under certain limiting conditions. Relaxation dispersions were measured acquiring a minimal quantity of points, within a reduced Larmor frequency range and, under inferior experimental conditions (in the presence of magnetic field in-homogeneity and lower power supply stability). A simplified model is discussed, showing practical advantages when fitting the data within the reduced frequency range. Experiments are contrasted with standard measurements performed in a state-of-the-art relaxometer. The methodology was tested in samples of 1,2-dimyristoyl-sn-glycero-3-phosphocholine with different percentiles of cholesterol. We observe a tendency to a decrease in κ with increasing temperature, and a tendency to increase with the cholesterol percentile.

Dry-cured ham tissue characterization by fast field cycling NMR relaxometry and quantitative magnetization transfer.

Fast field cycling (FFC) and quantitative magnetization transfer (qMT) NMR methods are two powerful tools in NMR analysis of biological tissues. The qMT method is well established in biomedical NMR applications, while the FFC method is often used in investigations of molecular dynamics on which longitudinal NMR relaxation times of the investigated material critically depend. Despite their proven analytical potential, these two methods were rarely used in NMR studies of food, especially when combined together. In our study, we demonstrate the feasibility of a combined FFC/qMT-NMR approach for the fast and nondestructive characterization of dry-curing ham tissues differing by protein content. The characterization is based on quantifying the pure quadrupolar peak area (area under the quadrupolar contribution of dispersion curve obtained by FFC-NMR) and the restricted magnetization pool size (obtained by qMT-NMR). Both quantities correlate well with concentration of partially immobilized, nitrogen-containing and proton magnetization exchanging muscle proteins. Therefore, these two quantities could serve as potential markers for dry-curing process monitoring. Copyright © 2016 John Wiley & Sons, Ltd.

Conformational Redistribution of Honey Components following Different Storage Conditions

The present study aims at the investigation of the changes in water distribution among the organic components of selected honey samples following honey storage at different temperatures. Results, achieved by application of fast field cycling NMR relaxometry, revealed that the organic constituents were homogeneously distributed within the whole samples stored at room temperature. Conversely, after four months of refrigeration at 4°C, the organic systems were included in persistent clusters, as a consequence of the water release due to the larger stability of the intramolecular interactions over the intermolecular ones. The new conformational arrangements of the honey constituents entailed enhancement of honey moisture content. For this reason, it can be suggested that honey refrigeration prior to storage at room temperature may be detrimental for its long-term storage. In fact, higher risk of fermentation may occur once the sample is warmed after the first refrigeration step.