Frequency offset dependence of adiabatic rotating frame relaxation rate constants: relevance to MRS investigations of metabolite dynamics in vivo.
ABSTRACT: In this work, we investigated the frequency-offset dependence of the rotating frame longitudinal (R(1ρ)) and transverse (R(2ρ)) relaxation rate constants when using hyperbolic-secant adiabatic full passage pulses or continuous-wave spin-lock irradiation. Phantom and in vivo measurements were performed to validate theoretical predictions of the dominant relaxation mechanisms existing during adiabatic full passage pulses when using different settings of the frequency offset relative to the carrier. In addition, adiabatic R(1ρ) and R(2ρ) values of total creatine and N-acetylaspartate were measured in vivo from the human brain at 4 T. When the continuous-wave pulse power was limited to safe specific absorption rates for humans, simulations revealed a strong dependence of R(1ρ) and R(2ρ) values on the frequency offset for both dipolar interactions and anisochronous exchange mechanisms. By contrast, theoretical and experimental results showed adiabatic R(1ρ) and R(2ρ) values to be practically invariant within the large subregion of the bandwidth of the hyperbolic-secant pulse where complete inversion was achieved. However, adiabatic R(1ρ) and R(2ρ) values of the methyl protons of total creatine (at 3.03 ppm) were almost doubled when compared with those of the methyl protons of N-acetylaspartate (at 2.01 ppm) in spite of the fact that these resonances were in the flat region of the inversion band of the adiabatic full passage pulses. We conclude that differences in adiabatic R(1ρ) and R(2ρ) values of human brain metabolites are not a result of their chemical shifts, but instead reflect differences in dynamics.
Project description:Although originally designed for broadband inversion and decoupling in NMR spectroscopy, recent methodological developments have introduced adiabatic fast passage (AFP) pulses into the field of protein dynamics. AFP pulses employ a frequency sweep, and have not only superior inversion properties with respect to offset effects, but they are also easily implemented into a pulse sequence. As magnetization is dragged from the +z to the -z direction, Larmor precession is impeded since magnetization becomes spin-locked, which is a potentially useful feature for the investigation of microsecond to millisecond dynamics. A major drawback of these pulses as theoretical prediction is concerned, however, results from their time-dependent offset: simulations of spin density matrices under the influence of a time-dependent Hamiltonian with non-commuting elements are costly in terms of computational time, rendering data analysis impracticable. In this paper we suggest several ways to reduce the computational time without compromising accuracy with respect to effects such as cross-correlated relaxation and modulation of the chemical shift.
Project description:An adiabatic MEscher-GArwood (MEGA)-editing scheme, using asymmetric hyperbolic secant editing pulses, was developed and implemented in a B1+-insensitive, 1D-semiLASER (Localization by Adiabatic SElective Refocusing) MR spectroscopic imaging (MRSI) sequence for the non-invasive mapping of ?-aminobutyric acid (GABA) over a whole brain slice. Our approach exploits the advantages of edited-MRSI at 7T while tackling challenges that arise with ultra-high-field-scans. Spatial-spectral encoding, using density-weighted, concentric circle echo planar trajectory readout, enabled substantial MRSI acceleration and an improved point-spread-function, thereby reducing extracranial lipid signals. Subject motion and scanner instabilities were corrected in real-time using volumetric navigators optimized for 7T, in combination with selective reacquisition of corrupted data to ensure robust subtraction-based MEGA-editing. Simulations and phantom measurements of the adiabatic MEGA-editing scheme demonstrated stable editing efficiency even in the presence of ±0.15?ppm editing frequency offsets and B1+ variations of up to ±30% (as typically encountered in vivo at 7T), in contrast to conventional Gaussian editing pulses. Volunteer measurements were performed with and without global inversion recovery (IR) to study regional GABA levels and their underlying, co-edited, macromolecular (MM) signals at 2.99?ppm. High-quality in vivo spectra allowed mapping of pure GABA and MM-contaminated GABA+ (GABA + MM) along with Glx (Glu + Gln), with high-resolution (eff. voxel size: 1.4 cm3) and whole-slice coverage in 24?min scan time. Metabolic ratio maps of GABA/tNAA, GABA+/tNAA, and Glx/tNAA were correlated linearly with the gray matter fraction of each voxel. A 2.15-fold increase in gray matter to white matter contrast was observed for GABA when enabling IR, which we attribute to the higher abundance of macromolecules at 2.99?ppm in the white matter than in the gray matter. In conclusion, adiabatic MEGA-editing with 1D-semiLASER selection is as a promising approach for edited-MRSI at 7T. Our sequence capitalizes on the benefits of ultra-high-field MRSI while successfully mitigating the challenges related to B0/B1+ inhomogeneities, prolonged scan times, and motion/scanner instability artifacts. Robust and accurate 2D mapping has been shown for the neurotransmitters GABA and Glx.
Project description:Three different techniques (adiabatic passage Hartman-Hahn cross-polarization, optimal control designed pulses, and EXPORT) are compared for transferring (15)N magnetization to (13)C in solid-state NMR experiments under magic-angle-spinning conditions. We demonstrate that, in comparison to adiabatic passage Hartman-Hahn cross-polarization, optimal control transfer pulses achieve similar or better transfer efficiencies for uniformly-(13)C,(15)N labeled samples and are generally superior for samples with non-uniform labeling schemes (such as 1,3- and 2-(13)C glycerol labeling). In addition, the optimal control pulses typically use substantially lower average RF field strengths and are more robust with respect to experimental variation and RF inhomogeneity. Consequently, they are better suited for demanding samples.
Project description:Mode-locked fiber lasers based on nonlinear polarization evolution can generate femtosecond pulses with different pulse widths and rich spectral distributions for versatile applications through polarization tuning. However, a precise and repeatable location of a specific pulsation regime is extremely challenging. Here, by using fast spectral analysis based on a time-stretched dispersion Fourier transform as the spectral discrimination criterion, along with an intelligent polarization search algorithm, for the first time, we achieved real-time control of the spectral width and shape of mode-locked femtosecond pulses; the spectral width can be tuned from 10 to 40?nm with a resolution of ~1.47?nm, and the spectral shape can be programmed to be hyperbolic secant or triangular. Furthermore, we reveal the complex, repeatable transition dynamics of the spectrum broadening of femtosecond pulses, including five middle phases, which provides deep insight into ultrashort pulse formation that cannot be observed with traditional mode-locked lasers.
Project description:The adiabatic manipulation of quantum states is a powerful technique that opened up new directions in quantum engineering--enabling tests of fundamental concepts such as geometrical phases and topological transitions, and holding the promise of alternative models of quantum computation. Here we benchmark the stimulated Raman adiabatic passage for circuit quantum electrodynamics by employing the first three levels of a transmon qubit. In this ladder configuration, we demonstrate a population transfer efficiency >80% between the ground state and the second excited state using two adiabatic Gaussian-shaped control microwave pulses. By doing quantum tomography at successive moments during the Raman pulses, we investigate the transfer of the population in time domain. Furthermore, we show that this protocol can be reversed by applying a third adiabatic pulse, we study a hybrid nondiabatic-adiabatic sequence, and we present experimental results for a quasi-degenerate intermediate level.
Project description:Slow micros/ms dynamics involved in protein folding, binding, catalysis, and allostery are currently detected using NMR dispersion experiments such as CPMG (Carr-Purcell-Meiboom-Gill) or spin-lock R(1rho). In these methods, protein dynamics are obtained by analyzing relaxation dispersion curves obtained from either changing the time spacing between 180 degree pulses or by changing the effective spin-locking field strength. In this Communication, we introduce a new method to induce a dispersion of relaxation rates. Our approach relies on altering the shape of the adiabatic full passage pulse and is conceptually different from existing approaches. By changing the nature of the adiabatic radiofrequency irradiation, we are able to obtain rotating frame R(1rho) and R(2rho) dispersion curves that are sensitive to slow micros/ms protein dynamics (demonstrated with ubiquitin). The strengths of this method are to (a) extend the dynamic range of the relaxation dispersion analysis, (b) avoid the need for multiple magnetic field strengths to extract dynamic parameters, (c) measure accurate relaxation rates that are independent of frequency offset, and (d) reduce the stress to NMR hardware (e.g., cryoprobes).
Project description:Accurate control of a quantum system is a fundamental requirement in many areas of modern science ranging from quantum information processing to high-precision measurements. A significantly important goal in quantum control is preparing a desired state as fast as possible, with sufficiently high fidelity allowed by available resources and experimental constraints. Stimulated Raman adiabatic passage (STIRAP) is a robust way to realize high-fidelity state transfer but it requires a sufficiently long operation time to satisfy the adiabatic criteria. Here we theoretically propose and then experimentally demonstrate a shortcut-to-adiabatic protocol to speed-up the STIRAP. By modifying the shapes of the Raman pulses, we experimentally realize a fast and high-fidelity stimulated Raman shortcut-to-adiabatic passage that is robust against control parameter variations. The all-optical, robust and fast protocol demonstrated here provides an efficient and practical way to control quantum systems.
Project description:NMR relaxation methods probe biomolecular motions over a wide range of timescales. In particular, the rotating frame spin-lock R(1?) and Carr-Purcell-Meiboom-Gill (CPMG) R(2) experiments are commonly used to characterize ?s to ms dynamics, which play a critical role in enzyme folding and catalysis. In an effort to complement these approaches, we introduced the Heteronuclear Adiabatic Relaxation Dispersion (HARD) method, where dispersion in rotating frame relaxation rate constants (longitudinal R(1?) and transverse R(2?)) is created by modulating the shape and duration of adiabatic full passage (AFP) pulses. Previously, we showed the ability of the HARD method to detect chemical exchange dynamics in the fast exchange regime (k(ex)?10(4)-10(5) s(-1)). In this article, we show the sensitivity of the HARD method to slower exchange processes by measuring R(1?) and R(2?) relaxation rates for two soluble proteins (ubiquitin and 10C RNA ligase). One advantage of the HARD method is its nominal dependence on the applied radio frequency field, which can be leveraged to modulate the dispersion in the relaxation rate constants. In addition, we also include product operator simulations to define the dynamic range of adiabatic R(1?) and R(2?) that is valid under all exchange regimes. We conclude from both experimental observations and simulations that this method is complementary to CPMG-based and rotating frame spin-lock R(1?) experiments to probe conformational exchange dynamics for biomolecules. Finally, this approach is germane to several NMR-active nuclei, where relaxation rates are frequency-offset independent.