Journal of Magnetic Resonance Open最新文献

Signal Amplification By Reversible Exchange (SABRE) is a technique aimed at enhancing weak NMR signals of heteronuclei by utilizing the non-equilibrium spin order of parahydrogen. SABRE polarization transfer takes place by means of metalorganic complexes that interact with parahydrogen and the substrate to be polarized in a reversible manner. To achieve substrate hyperpolarization in the high magnetic field of an NMR magnet, radiofrequency (RF) excitation is required. There are two general options for the RF field amplitude: constant or modulated. To date, there has been limited optimization of the adiabatic SABRE conditions. In SABRE, the presence of chemical exchange significantly complicates the spin dynamics involved in polarization transfer and the optimization of adiabatic RF sweeps. We conducted a comprehensive analysis of high-field SABRE pulse sequences with RF sweeps on the heteronuclear channel, specifically ¹⁵N. We proposed a simple method for optimizing the amplitude modulation profile of the RF field, which is efficient for systems undergoing chemical exchange. Our approach involved utilizing the dependence of ¹⁵N polarization on the amplitude of the constant RF field on the ¹⁵N channel. By employing the "optimal" adiabatic RF profile, we achieved a 2.5-fold increase in ¹⁵N SABRE-derived polarization at high magnetic field compared to a linear sweep. We theoretically assessed the benefit of RF sweeps over constant RF fields for SABRE at high magnetic field. We demonstrated experimentally that at temperatures $-5^{\circ }$C - $+{10}^{\circ }$C RF sweeps are more efficient than constant RF field. Maximal increase in ¹⁵N polarization achieved was 1.7-fold for bound and 1.4-fold for free substrate. We attribute this increase in polarization to the adiabaticity of the polarization transfer process. This behavior was explained via numerical solution of SABRE master equation for different dissociation rate constants.

Commercial availability, ease of printing and cost effectiveness have rendered 3D printing an essential part of magnetic resonance (MR) experimental design. However, the magnetic properties of several materials contemporarily used for 3D printing are lacking in literature to some extent. A database of the magnetic susceptibilities of several commonly used 3D printing materials is provided, which may aid MR experiment design. Here, we exploit the capability of magnetic resonance imaging (MRI) to map the local magnetic field variations caused by these materials when placed in the scanner's B₀ field. Exact analytical solutions of the magnetic flux density distribution for a cylindrical geometry are utilized to fit experimentally obtained data with theory in order to quantify the magnetic susceptibilities. A detailed explanation of the data processing and fitting procedure is presented and validated by measuring the susceptibility of air along with high resolution MR measurements. Furthermore, an initiative is taken to address the need for a comprehensive database comprising of not only the magnetic susceptibilities of 3D printing materials, but also information on the 3D printing parameters, the printers used, and other information available for the materials that may also influence the measured magnetic properties. An open platform with the magnetic susceptibilities of materials reported in this work besides existing literature values is provided here, with the aim to invite researchers to enable further extension and development towards an open database to characterize commonly used 3D printing materials based on their magnetic properties.

Magnetic resonance imaging is a powerful, non invasive tool for medical diagnosis. The low sensitivity for detecting the nuclear spin signals, typically limits the image resolution to several tens of micrometers in preclinical systems and millimeters in clinical scanners. Other sources of information, derived from diffusion processes of intrinsic molecules such as water in the tissues, allow getting morphological information at micrometric and submicrometric scales as potential biomarkers of several pathologies. Here we consider extracting this morphological information by probing the distribution of internal magnetic field gradients induced by the heterogeneous magnetic susceptibility of the medium. We use a cumulant expansion to derive the dephasing on the spin signal induced by the molecules that explore these internal gradients while diffusing. Based on the cumulant expansion, we define internal gradient distributions tensors (IGDT) and propose modulating gradient spin echo sequences to probe them. These IGDT contain microstructural morphological information that characterize porous media and biological tissues. We evaluate the IGDT effects on the magnetization decay with typical conditions of brain tissue and show that their effects can be experimentally observed. Our results thus provide a framework for exploiting IGDT as quantitative diagnostic tools.

An electron spin echo in a nitroxide-containing polymer cathode film for organic radical batteries is observed for various states of charge at cryogenic temperatures. The EPR-detected state of charge (ESOC), as inferred from the number of paramagnetic centers in the film, is compared to the results of Coulomb counting based on galvanostatic charging. Spin concentration, longitudinal relaxation times $T_1$ and phase memory times $T_m$ strongly correlate with the ESOC. In the discharged film, the spin concentration reaches $\left(5\pm 3\right)\times 10^{20}$ cm⁻³, causing a phase memory time $T_m\ll$ 100 ns (shorter than the resonator ring-down time) that hinders the detection of the spin echo. In the charged film, the decreased spin concentration results in a longer $T_m$ between 100 ns and 300 ns that enables spin-echo detection, yet limits the length of the microwave pulse sequence. The short, broad-band pulses cause instantaneous diffusion in the unoxidized domains across the oxidized film, affecting the relative peak intensities in the pulsed EPR spectrum. By simulating the spectral distortion caused by instantaneous diffusion, we obtain information on the local spin concentration, which complements the information on the ‘bulk’ spin concentration determined by electrochemistry and continuous-wave EPR spectroscopy.

This study investigates the experimental conditions required for magnetic resonance imaging (MRI) of thermally polarized hydrocarbon gas, focusing on ethane. The nuclear magnetic resonance (NMR) spectra and relaxation properties of ethane were analysed at different pressures in the range from 1.5 to 6 bar at 7 T using ¹H NMR spectroscopy. The spin-lattice relaxation time (T₁) and spin-spin relaxation time (T₂) were measured, and their dependence on the pressure was determined, showing that both relaxation times increase with pressure. Using the estimated relaxation times, we adjusted parameters for imaging of static ethane using rapid acquisition with relaxation enhancement (RARE) and fast low-angle shot (FLASH). The signal-to-noise ratio (SNR) of ethane images was evaluated and compared to the calculation for the given range of pressures. Then, we imaged flowing gas using a 2D velocity-encoded pulse sequence, which is usually used for liquid flow studies. The MRI-measured flow rates are compared to those pre-set with a pump, showing good agreement in the slow flow range. Overall, the results provide insights into the feasibility of ¹H MRI for imaging and flow measurements of thermally polarized ethane.

Parahydrogen-Induced Polarization (PHIP) is NMR hyperpolarization technique that has matured from fundamental science to a biomedical tool for production of hyperpolarized MRI contrast agents. The spin order of nascent parahydrogen-derived protons can be employed directly for enhancement of their NMR signals or for polarization transfer to other nuclei in the hydrogenation product. In this work, we study the process of pairwise parahydrogen addition to propylene, which results in symmetric propane molecule with substantially enhanced methyl and methylene NMR signals. Specifically, we have synthesized site-selectively isotopically labeled 3-d-propylene molecule to study polarization dynamics in the resulting monodeuterated propane after pairwise parahydrogen addition. The deuterium presence in the hyperpolarized propane product results in a minute isotope chemical shift effect allowing to distinguish the proton resonances of CH₃ and CH₂D groups at 600 MHz. Pairwise parahydrogen 1,2-addition to 3-d-propylene was first confirmed by performing the reaction inside a 600 MHz NMR spectrometer, i.e., in the weakly-coupled regime at 14 T, where proton polarization dynamics is restricted to the molecular sites of parahydrogen addition. However, when the pairwise parahydrogen addition is performed in the strongly-coupled regime, i.e., at the Earth's magnetic field, efficient polarization transfer to CH₂D protons is readily observed, leading to polarization redistribution between the three inequivalent sites. This finding is important as it sheds light on polarization dynamics in the strongly coupled symmetric spin systems such as propane studied here—the presented results are expected to be applicable to other spin systems such as butane.

In this work, we describe essential tools of linear algebra necessary for calculating the effect of chemical exchange on spin dynamics and polarization transfer in various nuclear magnetic resonance (NMR) experiments. We show how to construct matrix representations of Hamiltonian, relaxation, and chemical exchange superoperators in both Hilbert and Liouville space, as well as demonstrate corresponding codes in Python. Examples of applying the code are given for problems involving chemical exchange between NH${}_3$ and NH${}_4^{+}$ at zero and high magnetic field and polarization transfer from parahydrogen relevant in SABRE (signal amplification by reversible exchange) at low magnetic field (0-20 mT). The presented methodology finds utility for describing the effect of chemical exchange on NMR spectra and can be extended further by taking into account non-linearities in the master equation.

Magnetic resonance offers an invaluable testbed for observing and studying the fundamental concepts of quantum cavity interactions with two-level systems in the microwave regime. Typically, these experiments are conducted at low cryogenic temperatures, utilizing spin systems embedded within a high-quality (Q-factor) superconducting cavity. Recent studies indicate that under these conditions, especially in a high-cooperativity regime with strong collective coupling between an electron spin system and a microwave cavity, multiple spin echoes can be detected. These echoes are interpreted as manifestations of coherent quantum effects. To put it simply, photons within the cavity can excite the spin system, which subsequently can stimulate the cavity, creating a feedback loop. In our research, we demonstrate that a specially designed moderate-Q cavity, paired with diamond crystals rich in nitrogen vacancy (NV) centers, allows us to observe such nonlinear quantum phenomena, even at ambient temperatures. Crucially, our experimental design necessitates amplifying the net number of spins for a specific, limited spin concentration. This is achieved by lowering the spins' thermodynamic temperature (as opposed to their physical temperature) to a few kelvins. Notably, we find that maintaining high cooperativity or strong coupling is not essential for these observations. The potential to observe significant microwave cavity quantum effects at room temperature could be useful for future applications, such as quantum memories and quantum sensing.

Hyperpolarization with the dissolution dynamic nuclear polarization (dDNP) technique yields > 10,000-fold signal increases for NMR-active nuclei (e.g. ¹³C). Hyperpolarized ¹³C-labeled metabolic tracer molecules thus allow real-time observations of biochemical pathways in living cellular systems without interfering background. This methodology lends itself to the direct observation of altered intracellular reaction chemistry imparted for instance by drug treatment, infections, or other diseases. A reoccurring challenge for longitudinal cell studies of mammalian cells with NMR and dDNP-NMR is maintaining cell viability in the NMR spectrometer. 3D cell culture methods are increasing in popularity because they provide a physiologically more relevant environment compared to 2D cell cultures. Based on such strategies a mobile 3D culture system was devised. The clinical drug etoposide was used to treat cancer cells (HeLa) and the resulting altered metabolism was measured using hyperpolarized [1–¹³C]pyruvate. We show that sustaining the cell cultivation in cell incubators and only transferring the cells to the NMR spectrometer for the few minutes required for the dDNP-NMR measurements is an attractive alternative to cell maintenance in the NMR tube. High cell viability is sustained, and experimental throughput is many doubled.