The Minimum Admissible Detuning Efficiency of MRI Receive-Only Surface Coils.

BACKGROUND: The minimum admissible detuning efficiency (DE) of a receive coil is an essential parameter for coil designers. A receive coil with inefficient detuning leads to inhomogeneous B1 during excitation. Previously proposed criteria for quantifying the DE rely on indirect measurements and are difficult to implement. PURPOSE: To present an alternative method to quantify the DE of receive-only surface coils. STUDY TYPE: Theoretical study supported by simulations and phantom experiments. PHANTOMS: Uniform spherical (100 mm diameter) and cylindrical (66 mm diameter) phantoms. FIELD STRENGTH/SEQUENCE: Dual repetition time B1 mapping sequence at 1.5T, and Bloch-Siegert shift B1 mapping sequence at 3.0T. ASSESSMENT: One non-planar (80 × 43 mm2) and two planar (40 and 57 mm diameter) surface coils were built. Theoretical analysis was performed to determine the minimum DE required to avoid B1 distortions. Experimental B1 maps were acquired for the non-planar and planar surface coils at both 1.5T and 3.0T and visually compared with simulated B1 maps to assess the validity of the theoretical analysis. STATISTICAL TESTS: None. RESULTS: Based on the theoretical analysis, the proposed minimum admissible DE, defined as DEthr = 20 Log (Q) + 13 dB, depended only on the quality factor (Q) of the coil and was independent of coil area and field strength. Simulations and phantom experiments showed that when the DE was higher than this minimum threshold level, the B1 field generated by the transmission coil was not modified by the receive coil. DATA CONCLUSION: The proposed criterion for assessing the DE is simple to measure, and does not depend on the area of the coil or on the magnetic field strength, up to 3T. Experimental and simulated B1 maps confirmed that detuning efficiencies above the theoretically derived minimal admissible DE resulted in a non-distorted B1 field. EVIDENCE LEVEL: 2 TECHNICAL EFFICACY: Stage 1.

Remotely detuned receiver coil for high-resolution interventional cardiac magnetic resonance imaging.

Introduction: Interventional cardiac MRI in the context of the treatment of cardiac arrhythmia requires submillimeter image resolution to precisely characterize the cardiac substrate and guide the catheter-based ablation procedure in real-time. Conventional MRI receiver coils positioned on the thorax provide insufficient signal-to-noise ratio (SNR) and spatial selectivity to satisfy these constraints. Methods: A small circular MRI receiver coil was developed and evaluated under different experimental conditions, including high-resolution MRI anatomical and thermometric imaging at 1.5 T. From the perspective of developing a therapeutic MR-compatible catheter equipped with a receiver coil, we also propose alternative remote active detuning techniques of the receiver coil using one or two cables. Theoretical details are presented, as well as simulations and experimental validation. Results: Anatomical images of the left ventricle at 170 µm in-plane resolution are provided on ex vivo beating heart from swine using a 2 cm circular receiver coil. Taking advantage of the increase of SNR at its vicinity (up to 35 fold compared to conventional receiver coils), real-time MR-temperature imaging can reach an uncertainty below 0.1°C at the submillimetric spatial resolution. Remote active detuning using two cables has similar decoupling efficiency to conventional on-site decoupling, at the cost of an acceptable decrease in the resulting SNR. Discussion: This study shows the potential of small dimension surface coils for minimally invasive therapy of cardiac arrhythmia intraoperatively guided by MRI. The proposed remote decoupling approaches may simplify the construction process and reduce the cost of such single-use devices.

Computational elucidation of the aging time effect on zeolite synthesis selectivity in the presence of water and diquaternary ammonium iodide.

An example of zeolite selectivity (MFI → MOR) driven by synthesis aging time has been studied. Using N,N,N',N'-tetramethyl-N,N'-dipropyl-ethylenediammonium diiodide (TMDP) as an organic structure-directing agent (OSDA), the zeolite phases obtained at 2 h (MFI 97%), 8 h (MFI 84%, MOR 16%) and 24 h (MFI 43%, MOR 57%) have been characterized by powder X-ray diffraction. The results suggest that at intermediate aging time, namely 8 h and 24 h, the dominant phase (MFI) is displaced by MOR. Different techniques (FT-IR, Raman, 13C MAS NMR, TGA/DTG and HC microanalysis) have been employed to verify the OSDA integrity and occlusion inside the zeolite micropores as well as to quantify the water and OSDA loading. The 1H MAS NMR of the as-made occluded zeolite was compared with the spectra of TMDP and the recovered OSDA from the sample by extraction with water. The comparison indicated that TMDP was not structurally intact, indicating the chemical transformation of TMDP to imidazolinium homologues through the Hofmann degradation process. Furthermore, careful acidic breakdown of the aluminosilicate shell, covered on the zeolite samples by hydrofluoric acid, revealed that the remaining OSDA had been partially degraded to lower molecular weight ammonium salt, confirmed by 1H NMR and mass spectrometry measurements. A computational study was performed by using a force field based methodology, including accurate loading of water and OSDA in the zeolite (MFI and MOR) unit cells. The results show an important contribution of the presence of water. The samples with larger aging time (8 h and 24 h) incorporate less water and show partial TMDP degradation, whilst at the shortest aging time (2 h), there is a larger water content and TMDP remains intact. The larger accessible volume of MFI justifies that this is the dominant phase at short aging times (large water content) since it can accommodate a larger number of water molecules than MOR. The OSDA partial degradation also plays a role. At longer aging times the partial OSDA decomposition has been considered in the models by including TMDP + Imidaz, which is more stabilized by MOR, whilst at shorter aging times the only OSDA present, TMDP, is better stabilized by MFI.

Spin Thermometry: A Straightforward Measure of Millikelvin Deuterium Spin Temperatures Achieved by Dynamic Nuclear Polarization.

Dynamic nuclear polarization of samples at low temperatures, typically between 1.2 and 4.2 K, allows one to achieve spin temperatures of as low as 2 mK so that for many nuclear isotopes the high-temperature approximation is violated for the nuclear Zeeman interaction. This leads to characteristic asymmetries in powder spectra. We show that the line shapes due to the quadrupolar couplings of deuterium spins present in virtually all solvents used for such experiments (DNP juice) allow the quick yet accurate determination of the deuterium spin temperature or, equivalently, the deuterium polarization. The observation of quadrupolar echoes excited by small flip-angle pulses allows one to monitor the build-up and decay of the positive or negative deuterium polarization.

Orientation-Dependent Proton Relaxation of Water Molecules Trapped in Solids: Crystallites with Long-Lived Magnetization.

The longitudinal spin-lattice relaxation properties of water molecules trapped in a static powdered polycrystalline sample of barium chlorate monohydrate are investigated by means of solid-state 1H NMR spectroscopy. Different portions of the inhomogeneous Pake pattern that are associated with crystallites at different orientations with respect to the external magnetic field show either a mono- or a biexponential recovery. At high field (9.4 T), the chemical shift anisotropy is the main interaction that is responsible for the inhomogeneity of the relaxation rates. A theoretical description of rapid two-site hopping about the H-O-H bisector in the framework of Liouville space agrees very well with the experimental evidence. Numerical simulations predict a distribution of monoexponential time constants associated with individual single-crystal orientations. Overlapping signals give rise to biexponential recovery. This is confirmed experimentally by 1H NMR spectra of static single crystals.

A Low-Temperature Broadband NMR Probe for Multinuclear Cross-Polarization.

Dissolution dynamic nuclear polarization (D-DNP) probes are usually designed for one or at most two specific nuclei. Investigation of multiple nuclei usually requires manufacturing a number of costly probes. In addition, changing the probe is a time-consuming process since a system that works at low temperature (usually between 1.2 and 4.2 K) must be warmed up, thus increasing the risks of contamination. Here, an efficient apparatus is described for D-DNP designed not only for microwave-enhanced direct observation of a wide range of nuclei S such as 1 H, 13 C, 2 H, 23 Na, and 17 O, but also for cross-polarization (CP) from I=1 H to such S nuclei. Unlike most conventional designs, the tuning and matching circuits are partly immersed in superfluid helium at temperatures down to 1.2 K. Intense radio-frequency (RF) fields with amplitudes on the order of 50 kHz or better can be applied simultaneously to both nuclei I and S using RF amplifiers with powers on the order of 90 and 80 W, respectively, without significant losses of liquid helium. The system can operate at temperatures over a wide range between 1.2 and 300 K.

Investigation of activation energies for dissociation of host-guest complexes in the gas phase using low-energy collision induced dissociation.

A low-energy collision induced dissociation (CID) (low-energy CID) approach that can determine both activation energy and activation entropy has been used to evaluate gas-phase binding energies of host-guest (H-G) complexes of a heteroditopic hemicryptophane cage host (Zn (II)@1) with a series of biologically relevant guests. In order to use this approach, preliminary calibration of the effective temperature of ions undergoing resonance excitation is required. This was accomplished by employing blackbody infrared radiative dissociation (BIRD) which allows direct measurement of activation parameters. Activation energies and pre-exponential factors were evaluated for more than 10 H-G complexes via the use of low-energy CID. The relatively long residence time of the ions inside the linear ion trap (maximum of 60 s) allowed the study of dissociations with rates below 1 s-1 . This possibility, along with the large size of the investigated ions, ensures the fulfilment of rapid energy exchange (REX) conditions and, as a consequence, accurate application of the Arrhenius equation. Compared with the BIRD technique, low-energy CID allows access to higher effective temperatures, thereby permitting one to probe more endothermic decomposition pathways. Based on the measured activation parameters, guests bearing a phosphate (-OPO3 2- ) functional group were found to bind more strongly with the encapsulating cage than those having a sulfonate (-SO3 - ) group; however, the latter ones make stronger bonds than those with a carboxylate (-CO2 - ) group. In addition, it was observed that the presence of trimethylammonium (-N(CH3 )3 + ) or phenyl groups in the guest's structure improves the strength of H-G interactions. The use of this technique is very straightforward, and it does not require any instrumental modifications. Thus, it can be applied to other H-G chemistry studies where comparison of bond dissociation energies is of paramount importance.

Advances in single-scan time-encoding magnetic resonance imaging.

Time-encoding MRI is a single-scan method that uses traditional k-encoding only in one direction. In the orthogonal "time-encoding" direction, a string of echoes appears in an order that depends on the position of the corresponding spin packets. In one variant of time-encoding, this is achieved by using a series of selective pulses and appropriate gradients in both k-encoding and time-encoding directions. Although time-encoding offers some advantages over traditional single-scan Fourier methods such as echo planar imaging (EPI), the original time-encoding sequence also has some drawbacks that limit its applications. In this work, we show how one can improve several aspects of the original time-encoding sequence. By using an additional gradient pulse one can change the order in which the echoes appear, leading to identical echo times for all echoes, and hence to a uniform signal attenuation due to transverse relaxation and a reduction in average signal attenuation due to diffusion. By rearranging positive and negative gradients one can reduce the switching rate of the gradients. Furthermore, we show how one can implement time-encoding sequences in an interleaved fashion in order to reduce signal attenuation due to transverse relaxation and diffusion, while increasing the spatial resolution.

Characterizing Thermal Mixing Dynamic Nuclear Polarization via Cross-Talk between Spin Reservoirs.

Dynamic nuclear polarization (DNP) embraces a family of methods to increase signal intensities in nuclear magnetic resonance (NMR) spectroscopy. Despite extensive theoretical work that allows one to distinguish at least five distinct mechanisms, it remains challenging to determine the relative weights of the processes that are responsible for DNP in state-of-the-art experiments operating with stable organic radicals like nitroxides at high magnetic fields and low temperatures. Specifically, determining experimental conditions where DNP involves thermal mixing, which denotes a spontaneous heat exchange between different spin reservoirs, remains challenging. We propose an experimental approach to ascertain the prevalence of the thermal mixing regime by monitoring characteristic signature properties of the time evolution of the hyperpolarization. We find that thermal mixing is the dominant DNP mechanism at high nitroxide radical concentrations, while a mixture of different mechanisms prevails at lower concentrations.

Susceptibility contrast by echo shifting in spatially encoded single-scan MRI.

To overcome the effects of static field inhomogeneities, single-scan hybrid imaging techniques that use k-space encoding in one direction and spatial encoding in the other have been shown to be superior to traditional imaging techniques based on full k-space encoding. Like traditional imaging methods, hybrid methods can be implemented in different ways that favor different sources of contrast. So far, little attention appears to have been paid to these aspects. By modifying an established hybrid imaging sequence called Rapid Acquisition by Sequential Excitation and Refocusing (RASER) so as to obtain Echo-Shifted RASER sequences, we show that by shifting spin echoes one can tune the contrast due to inhomogeneous T decay.

The effects of molecular diffusion in spatially encoded magnetic resonance imaging.

In spatially encoded MRI, the signal is acquired sequentially for different coordinates. In particular for single-scan acquisitions in inhomogeneous fields, spatially encoded methods improve the image quality compared to traditional k-space encoding. Previously, much attention has been paid in order to homogenize T2 losses across the sample. In this work, we investigate the effects of diffusion on the image quality in spatially encoded MRI. We show that losses due to diffusion are often not uniform along the spatially encoded dimension, and how to adapt spatially encoded sequences in order to obtain uniformly diffusion-weighted images.

Dissolution dynamic nuclear polarization of deuterated molecules enhanced by cross-polarization.

We present novel means to hyperpolarize deuterium nuclei in 13CD2 groups at cryogenic temperatures. The method is based on cross-polarization from 1H to 13C and does not require any radio-frequency fields applied to the deuterium nuclei. After rapid dissolution, a new class of long-lived spin states can be detected indirectly by 13C NMR in solution. These long-lived states result from a sextet-triplet imbalance (STI) that involves the two equivalent deuterons with spin I = 1. An STI has similar properties as a triplet-singlet imbalance that can occur in systems with two equivalent I = 12 spins. Although the lifetimes TSTI are shorter than T1(Cz), they can exceed the life-time T1(Dz) of deuterium Zeeman magnetization by a factor of more than 20.