From LASER physics to the para-hydrogen pumped RASER.

The properties of the LASER with respect to self-organization are compared with the key features of the p-H2 pumped RASER. According to LASER theory the equations of motion for the LASER can be derived from the enslaving principle, i.e. the slowest-changing order parameter (the light field in the resonator) enslaves the rapidly relaxing atomic degrees of freedom. Likewise, it is shown here that the equations of motion for the p-H2 pumped RASER result from a set of order parameters, where the transverse magnetization of the RASER-active spin states enslaves the electromagnetic modes. The consequences are striking for nuclear magnetic resonance (NMR) spectroscopy, since long-lasting multi-mode RASER oscillations enable unprecedented spectroscopic resolution down to the micro-Hertz regime. Based on the theory for multi-mode RASER operation we analyze the conditions that reveal either the collapse of the entire NMR spectrum, the occurrence of self-organized frequency-combs, or RASER spectra which reflect the J-coupled network of the molecule. Certain RASER experiments involving the protons of 15N pyridine or 3-picoline molecules pumped with p-H2 via SABRE (Signal Amplification By Reversible Exchange) show either a single RASER oscillation in the time domain, giant RASER pulses or a complex RASER beat pattern. The corresponding 1H spectra consist of one narrow line, equidistant narrow lines (frequency-comb), or highly resolved lines reporting NMR properties, respectively. Numerous applications in the areas of material sciences, fundamental physics and medicine involving high precision sensors for magnetic fields, rotational motions or molecular structures become feasible.

Polarization transfer efficiency in PHIP experiments.

Parahydrogen induced polarization (PHIP) is a hyperpolarization method for NMR signal enhancement with applications in spectroscopy and imaging. Although parahydrogen can be easily enriched up to nearly 95%, the polarization detected on the hydrogenated substrate is substantially lower, where numerous loss mechanisms between the start of the hydrogenation reaction and detection affect polarization levels. The quality of PHIP systems is commonly determined by stating either the polarization degree or the enhancement factor of the product at the time of detection. In this study, we present a method that allows the distinction of polarization loss due to both the catalytic cycle and T1 relaxation of the formed product prior to detection. We determine the influence of homogeneous catalysts and define a rigorous measure of the polarization transfer efficiency (PTE). Our results show that the PTE strongly depends on the concentration of all components and the chemical structure of the catalyst as well as on the magnetic field of detection.

Moisture dynamics in wall paintings monitored by single-sided NMR.

The durability of historic wall paintings is highly dependent on environmental influences such as moisture ingress, salt crystallization and temperature changes. A fundamental understanding of dynamic transport processes in wall paintings is necessary to apply suitable conservation and restoration methods to preserve such objects with high cultural value. Non-invasive, mobile-NMR techniques with single-sided sensors, such as the NMR-MOUSE(®), enable to monitor the moisture content, transport and apparent diffusion constants in wall paintings. We investigated this technique by experiment and modeling to correlate salt crystallization, moisture transport and local diffusion in wall-painting samples. Moreover, the influence of different painting techniques (fresco and secco) and conservation/consolidation methods on moisture transport and diffusion is discussed. The results are compared with results from field measurements on real fresco paintings in Casa del Salone Nero and the Villa of the Papyri, Herculaneum, Italy.

On-line monitoring of chemical reactions by using bench-top nuclear magnetic resonance spectroscopy.

Real-time nuclear magnetic resonance (NMR) spectroscopy measurements carried out with a bench-top system installed next to the reactor inside the fume hood of the chemistry laboratory are presented. To test the system for on-line monitoring, a transfer hydrogenation reaction was studied by continuously pumping the reaction mixture from the reactor to the magnet and back in a closed loop. In addition to improving the time resolution provided by standard sampling methods, the use of such a flow setup eliminates the need for sample preparation. Owing to the progress in terms of field homogeneity and sensitivity now available with compact NMR spectrometers, small molecules dissolved at concentrations on the order of 1 mmol L(-1) can be characterized in single-scan measurements with 1 Hz resolution. Owing to the reduced field strength of compact low-field systems compared to that of conventional high-field magnets, the overlap in the spectrum of different NMR signals is a typical situation. The data processing required to obtain concentrations in the presence of signal overlap are discussed in detail, methods such as plain integration and line-fitting approaches are compared, and the accuracy of each method is determined. The kinetic rates measured for different catalytic concentrations show good agreement with those obtained with gas chromatography as a reference analytical method. Finally, as the measurements are performed under continuous flow conditions, the experimental setup and the flow parameters are optimized to maximize time resolution and signal-to-noise ratio.

Analysis of parahydrogen polarized spin system in low magnetic fields.

Nuclear magnetic resonance (NMR) spectra of spin systems polarized either thermally or by parahydrogen exhibit strikingly different field dependencies. Thermally polarized spin systems show the well-known roof effect, observed when reducing magnetic field strengths which precludes the independent determination of chemical shift differences and J-coupling constants at low-fields. Quantum mechanical analysis of the NMR spectra with respect to polarization method, pulsed state preparation, and transition probabilities reveals that spectra of parahydrogen polarized systems feature an "inverse roof effect" in the regime where the chemical shift difference δν is smaller than J. This inverse roof effect allows for the extraction of both J-coupling and chemical shift information down to very low fields. Based on a two-spin system, the observed non-linear magnetic field dependence of the splitting of spectral lines is predicted. We develop a general solution for the steady state density matrix of a parahydrogen polarized three-spin system including a heteronucleus which allows explaining experimentally observed (1)H spectra. The analysis of three-spin density matrix illustrates two pathways for an efficient polarization transfer from parahydrogen to (13)C nuclei. Examination of the experimental data facilitates the extraction of all relevant NMR parameters using single-scan, high-resolution (1)H and (13)C NMR spectroscopy at low fields at a fraction of the cost associated with cryogenically cooled high-field NMR spectrometers.

Highly stable and finely tuned magnetic fields generated by permanent magnet assemblies.

Permanent magnetic materials are the only magnetic source that can be used to generate magnetic fields without power consumption or maintenance. Such stand-alone magnets are very attractive for many scientific and engineering areas, but they suffer from poor temporal field stability, which arises from the strong sensitivity of the magnetic materials and mechanical support to temperature variation. In this work, we describe a highly efficient method useful to cancel the temperature coefficient of permanent magnet assemblies in a passive and accurate way. It is based on the combination of at least two units made of magnetic materials with different temperature coefficients arranged in such a way that the ratio of the fields generated by each unit matches the ratio of their effective temperature coefficients defined by both the magnetic and mechanical contributions. Although typically available magnetic materials have negative temperature coefficients, the cancellation is achieved by aligning the fields generated by each unit in the opposite direction. We demonstrate the performance of this approach by stabilizing the field generated by a dipolar Halbach magnet, recently proposed to achieve high field homogeneity. Both the field drift and the homogeneity are monitored via nuclear magnetic resonance spectroscopy experiments. The results demonstrate the compatibility of the thermal compensation approach with existing strategies useful to fine-tune the spatial dependence of the field generated by permanent magnet arrays.

Estimation of self-diffusion coefficients of small penetrants in semicrystalline polymers using single-sided NMR.

A simple and fast way to measure proton self-diffusion coefficients of small penetrant molecules in semicrystalline polymers is introduced. The approach takes advantage of the strong static gradient of a mobile single-sided NMR sensor and it is demonstrated on PE samples with varying degrees of crystallinity fully saturated in either toluene or n-hexane. The self-diffusion coefficients were measured using the gradient stimulated echo sequence appended with a CPMG. It is also shown for the first time, with demonstration on PE plates several millimeter thick with different aging histories, that one-dimensional profiles of self-diffusion coefficients as a function of depth can be easily obtained.

Studies of 6Li-NMR properties in different salt solutions in low magnetic fields.

In this article we report the longitudinal relaxation times (T(1)) of various (6)Li salts ((6)LiI, (6)LiCl and (6)LiNO(3)) in D(2)O and H(2)O, measured in low magnetic fields (B(0)=3.5mT). This investigation serves the purpose of clarifying the relaxation behavior of different (6)Li solutions and different concentrations. The measurement were undertaken to establish a framework for future applications of hyperpolarized (6)Li in medical imaging, biological studies and investigations of lithium ion batteries. Time will pass during the transport of hyperpolarized lithium ions to the sample, which leads to a polarization loss. In order to store polarization as long as possible, it is necessary to examine which (6)Li salt solution has the longest relaxation time T(1). Longitudinal relaxation times of (6)Li salts in D(2)O and H(2)O were investigated as a function of concentration and the most extended T(1) was found for (6)LiI in D(2)O and H(2)O. In agreement with the theory the relaxation time T(1) of all (6)Li salts increase with decreasing concentration. In the case of (6)LiI in H(2)O an inverse behavior was observed. We assume that the prolonged T(1) times occur due to formation of (6)LiOH upon the solution of (6)LiI in H(2)O, which settles as a precipitate. By diluting the solution, the precipitate continuously dissolves and approaches T(1) of (6)LiOH (T(1)∼28s), leading to a shorter T(1) relaxation time.

Near-zero-field nuclear magnetic resonance.

We investigate nuclear magnetic resonance (NMR) in near zero field, where the Zeeman interaction can be treated as a perturbation to the electron mediated scalar interaction (J coupling). This is in stark contrast to the high-field case, where heteronuclear J couplings are normally treated as a small perturbation. We show that the presence of very small magnetic fields results in splitting of the zero-field NMR lines, imparting considerable additional information to the pure zero-field spectra. Experimental results are in good agreement with first-order perturbation theory and with full numerical simulation when perturbation theory breaks down. We present simple rules for understanding the splitting patterns in near-zero-field NMR, which can be applied to molecules with nontrivial spectra.

Monitoring mass transport in heterogeneously catalyzed reactions by field-gradient NMR for assessing reaction efficiency in a single pellet.

An important aspect in assessing the performance of a catalytically active reactor is the accessibility of the reactive sites inside the individual pellets, and the mass transfer of reactants and products to and from these sites. Optimal design often requires a suitable combination of micro- and macropores in order to facilitate mass transport inside the pellet. In an exothermic reaction, fluid exchange between the pellet and the surrounding medium is enhanced by convection, and often by the occurrence of gas bubbles. Determining mass flow in the vicinity of a pellet thus represents a parameter for quantifying the reaction efficiency and its dependence on time or external reaction conditions. Field gradient Nuclear Magnetic Resonance (NMR) methods are suggested as a tool for providing parameters sensitive to this mass flow in a contact-free and non-invasive way. For the example of bubble-forming hydrogen peroxide decomposition in an alumina pellet, the dependence of the mean-squared displacement of fluid molecules on spatial direction, observation time and reaction time is presented, and multi-pulse techniques are employed in order to separate molecular displacements from coherent and incoherent motion on the timescale of the experiment. The reaction progress is followed until the complete decomposition of H2O2.

The heterogeneity of segmental dynamics of filled EPDM by (1)H transverse relaxation NMR.

Residual second moment of dipolar interactions M(2) and correlation time segmental dynamics distributions were measured by Hahn-echo decays in combination with inverse Laplace transform for a series of unfilled and filled EPDM samples as functions of carbon-black N683 filler content. The fillers-polymer chain interactions which dramatically restrict the mobility of bound rubber modify the dynamics of mobile chains. These changes depend on the filler content and can be evaluated from distributions of M(2). A dipolar filter was applied to eliminate the contribution of bound rubber. In the first approach the Hahn-echo decays were fitted with a theoretical relationship to obtain the average values of the (1)H residual second moment and correlation time <τ(c)>. For the mobile EPDM segments the power-law distribution of correlation function was compared to the exponential correlation function and found inadequate in the long-time regime. In the second approach a log-Gauss distribution for the correlation time was assumed. Furthermore, using an averaged value of the correlation time, the distributions of the residual second moment were determined using an inverse Laplace transform for the entire series of measured samples. The unfilled EPDM sample shows a bimodal distribution of residual second moments, which can be associated to the mobile polymer sub-chains (M(2) ≅ 6.1 rad (2) s(-2)) and the second one associated to the dangling chains M(2) ≅ 5.4 rad(2) s(-2)). By restraining the mobility of bound rubber, the carbon-black fillers induce diversity in the segmental dynamics like the apparition of a distinct mobile component and changes in the distribution of mobile and free-end polymer segments.

Structure and dynamics of water in native and tanned collagen fibers: Effect of crosslinking.

The influence of crosslinking on the hydration structure of collagen has been investigated. Nuclear magnetic resonance, dielectric relaxation and thermoporometry were used to investigate water structure in native and crosslinked collagen fibers on both wet and dried specimen. Measurements reveal the influence of different chemical treatments on the transverse relaxation time and polarization of the collagen fibers. The frequency dependence of dielectric constant of collagen fibers displays an induction behavior on low frequencies. Bound water constrained in collagen fibers seems to provide signatures for changes induced by crosslinking agents on the pore diameter and distribution in collagen fibers. A correlation of transverse relaxation time of water in dry and wet states presented in this study presents an experimental tool for examining the differences in efficacy of crosslinking agents. Changes in the dielectric relaxation, dynamics of water structure and hydroporometric structure of collagen are dependent on the nature of crosslinking material.

Chain dynamics of a weakly adsorbing polymer in thin films.

Thin films of weakly adsorbing poly(dimethyl siloxane) (PDMS) on porous alumina are examined with NMR fast field cycling (FFC) relaxometry and NMR transverse relaxometry. The longitudinal relaxation dispersion of polymer amounts corresponding to approximate monolayer coverage shows substantial deviation from the bulk and is characterized by a particularly weak temperature dependence. Thicker films, however, show relaxation behavior and temperature dependence more similar to the bulk polymer. Transverse relaxation times were found to cover a range of several orders of magnitudes for any sample investigated; their dependence on temperature is a function of the total amount of adsorbed polymer. While thick films see an overall increase of molecular mobility at higher temperatures, monolayer films are best characterized by the decreasing fraction of a short, i.e. relatively rigid, component. These effects are consistent with the concept of two regions, one in which chain dynamics deviate from bulk and another where chain dynamics are reduced but bulk-like, although chains inside each region may also experience motional heterogeneity.

Distributions of transverse relaxation times for soft-solids measured in strongly inhomogeneous magnetic fields.

The single-sided NMR-MOUSE sensor that operates in highly inhomogeneous magnetic fields is used to record a CPMG (1)H transverse relaxation decay by CPMG echo trains for a series of cross-linked natural rubber samples. Effective transverse relaxation rates 1/T(2,short) and 1/T(2,long) were determined by a bi-exponential fit. A linear dependence of transverse relaxation rates on cross-link density is observed for medium to large values of cross-link density. As an alternative to multi-exponential fits the possibility to analyze the dynamics of soft polymer network in terms of multi-exponential decays via the inverse Laplace transformation was studied. The transient regime and the effect of the T(1)/T(2) ratio in inhomogeneous static and radiofrequency magnetic fields on the CPMG decays were studied numerically using a dedicated C++ program to simulate the temporal and spatial dependence of the CPMG response. A correction factor T(2)/T(2,eff) is derived as a function of the T(1)/T(2) ratio from numerical simulations and compared with earlier results from two different well logging devices. High-resolution T(1)-T(2) correlations maps are obtained by two-dimensional Laplace inversion of CPMG detected saturation recovery curves. The T(1)-T(2) experimental correlations maps were corrected for the T(1)/T(2) effect using the derived T(2)/T(2,eff) correction factor.

Temperature stability and photodimerization kinetics of beta-cinnamic acid and comparison to its alpha-polymorph as studied by solid-state NMR spectroscopy techniques and DFT calculations.

Photoreactions of the alpha- and beta-polymorphs of trans-cinnamic acid were studied by (13)C CPMAS solid-state nuclear magnetic resonance spectroscopy, and the reactants and products were spectroscopically characterized in detail. Chemical shifts and chemical shift anisotropy tensors calculated using density functional theory (DFT) were found to be in good agreement with the experimental results and helped to identify the polymorphs and the individual assignments of reactant and photoproduct carbon atoms. The beta-polymorph is metastable. Its transformation into the alpha-cinnamic acid polymorph is monitored by temperature-dependent (13)C NMR spectroscopy. The transformation occurs at a very slow rate at room temperature but is highly accelerated at elevated temperatures. Analysis of the kinetics of the photoreaction shows that the beta-polymorph progresses at a slower rate compared to that of alpha-cinnamic acid. Based on chemical shift tensor values of reactants and products as obtained from 2D PASS spectra, the difference in reaction rates is suggested to be due to the higher amount of molecular reorientation of functional groups upon photoreaction and the larger distance between the reacting double bonds.

NMR investigations of polymer dynamics in a partially filled porous matrix.

The interior surface of well-defined porous alumina membranes (Anopore) of 20 nm and 200 nm pore diameter, respectively, was coated with polymer layers generated from solution by the solvent evaporation method. Deposits of poly(dimethyl siloxane) (PDMS) with nominal thicknesses ranging from 0.15 to 4.5 nm --corresponding to submonolayer to multilayer films--were investigated, and were compared to poly(butadiene) (PB) as an example for non-wetting polymers. Molecular weights below and above the critical value were studied since the bulk dynamics of such polymers are known to be qualitatively different. First results of NMR relaxation dispersion experiments on these systems are presented, supplemented by transverse relaxation times and double-quantum measurements obtained from high-field NMR. A systematic decrease of relaxation times at low fields with decreasing polymer amount is found for PDMS, but molecules retain a high degree of mobility irrespective of molecular weight. The relaxation dispersion results are supported by T2 data and 1H residual dipolar coupling (RDC) constants, and are discussed in terms of molecular order and reorientational dynamics.

Surface UV aging of elastomers investigated with microscopic resolution by single-sided NMR.

Depth profiles taken from the surface of UV irradiated natural rubber sheets have been measured with microscopic resolution using a Profile NMR-MOUSE. An NMR observable related to the sum of the spin echoes in the Carr-Purcell-Meiboom-Gill pulse sequence was used to characterize the cross-link density changes produced by the action of UV radiation in each sheet. The aging process was investigated as function of irradiation time and penetration depth. An exponential attenuation law with a space dependent absorption coefficient describes the change in the NMR observable with penetration depth. An Avrami model is used to describe the dependence of the absorption coefficient on the aging time. The method can be applied to investigate the effect of various aging agents on the surfaces of elastomers.

Hole-burning NMR in strongly inhomogeneous fields.

Different pulse sequences for frequency-selective NMR in the highly inhomogeneous fields of single-sided NMR are explored. A modified Hahn-echo is used to burn a hole in the spectrum of the detected echo. The hole diminishes following molecular dynamics on the scale of the echo time. Preliminary experiments were performed on pure water and natural rubber with the NMR-MOUSE. The results demonstrate the feasibility of hole burning to study slow molecular dynamics by mobile NMR in strongly inhomogeneous magnetic fields.

Study of order and dynamic processes in tendon by NMR and MRI.

Tendons are composed of a parallel arrangement of densely packed collagen fibrils that results in unique biomechanical properties of strength and flexibility. In the present review we discuss several advanced magnetic resonance spectroscopy (MRS) and imaging (MRI) techniques that have allowed us to better understand the biophysical properties of tendons and ligaments. The methods include multiple quantum and T(2) filtering combined with NMR and MRI techniques. It is shown in detail how these techniques can be used to extract a number of useful parameters: 1) the (1)H-(1)H and (1)H-(2)H dipolar interactions; 2) the proton exchange rates between water and collagen, and between water molecules; 3) the distribution of fibril orientations; and 4) the anisotropy of diffusion. It is shown that relaxation data as a function of angular dependence can be obtained in vivo using mobile NMR sensors. Finally, this article describes how double quantum filtered (DQF) MRI can be used to image and monitor the healing process in injured tendons.

Multiecho sequence for velocity imaging in inhomogeneous rf fields.

The unambiguous determination of velocities with spatial resolution in a multiecho PFG NMR sequence strongly depends on the homogeneity of the B1 field. This affects, in particular, the use of surface coils that bear considerable potential for on-line flow monitoring where a fast-imaging sequence can become vital. However, even with most rf coils dedicated for imaging applications, B1 inhomogeneities are sufficiently large to generate severe problems in performing velocity-imaging experiments. In this paper, the use of a combination of different phase cycles in Carr-Purcell sequences is discussed. The suggested phase cycling scheme tolerates large flip angle imperfections arising in inhomogeneous B1 fields, and thus allows acquisition of a maximum number of echoes within a pulse train. The performance of the velocity-imaging sequence is proven by using phantom samples developing known laminar flow patterns.