Internal gradient distributions: A susceptibility-derived tensor delivering morphologies by magnetic resonance.

Nuclear magnetic resonance is a powerful tool for probing the structures of chemical and biological systems. Combined with field gradients it leads to NMR imaging (MRI), a widespread tool in non-invasive examinations. Sensitivity usually limits MRI's spatial resolution to tens of micrometers, but other sources of information like those delivered by constrained diffusion processes, enable one extract morphological information down to micron and sub-micron scales. We report here on a new method that also exploits diffusion - isotropic or anisotropic- to sense morphological parameters in the nm-mm range, based on distributions of susceptibility-induced magnetic field gradients. A theoretical framework is developed to define this source of information, leading to the proposition of internal gradient-distribution tensors. Gradient-based spin-echo sequences are designed to measure these new observables. These methods can be used to map orientations even when dealing with unconstrained diffusion, as is here demonstrated with studies of structured systems, including tissues.

Local and bulk (13)C hyperpolarization in nitrogen-vacancy-centred diamonds at variable fields and orientations.

Polarizing nuclear spins is of fundamental importance in biology, chemistry and physics. Methods for hyperpolarizing (13)C nuclei from free electrons in bulk usually demand operation at cryogenic temperatures. Room temperature approaches targeting diamonds with nitrogen-vacancy centres could alleviate this need; however, hitherto proposed strategies lack generality as they demand stringent conditions on the strength and/or alignment of the magnetic field. We report here an approach for achieving efficient electron-(13)C spin-alignment transfers, compatible with a broad range of magnetic field strengths and field orientations with respect to the diamond crystal. This versatility results from combining coherent microwave- and incoherent laser-induced transitions between selected energy states of the coupled electron-nuclear spin manifold. (13)C-detected nuclear magnetic resonance experiments demonstrate that this hyperpolarization can be transferred via first-shell or via distant (13)Cs throughout the nuclear bulk ensemble. This method opens new perspectives for applications of diamond nitrogen-vacancy centres in nuclear magnetic resonance, and in quantum information processing.

QUANTUM SIMULATION. Localization-delocalization transition in the dynamics of dipolar-coupled nuclear spins.

Nonequilibrium dynamics of many-body systems are important in many scientific fields. Here, we report the experimental observation of a phase transition of the quantum coherent dynamics of a three-dimensional many-spin system with dipolar interactions. Using nuclear magnetic resonance (NMR) on a solid-state system of spins at room-temperature, we quench the interaction Hamiltonian to drive the evolution of the system. Depending on the quench strength, we then observe either localized or extended dynamics of the system coherence. We extract the critical exponents for the localized cluster size of correlated spins and diffusion coefficient around the phase transition separating the localized from the delocalized dynamical regime. These results show that NMR techniques are well suited to studying the nonequilibrium dynamics of complex many-body systems.

Size Distribution Imaging by Non-Uniform Oscillating-Gradient Spin Echo (NOGSE) MRI.

Objects making up complex porous systems in Nature usually span a range of sizes. These size distributions play fundamental roles in defining the physicochemical, biophysical and physiological properties of a wide variety of systems - ranging from advanced catalytic materials to Central Nervous System diseases. Accurate and noninvasive measurements of size distributions in opaque, three-dimensional objects, have thus remained long-standing and important challenges. Herein we describe how a recently introduced diffusion-based magnetic resonance methodology, Non-Uniform-Oscillating-Gradient-Spin-Echo (NOGSE), can determine such distributions noninvasively. The method relies on its ability to probe confining lengths with a (length)6 parametric sensitivity, in a constant-time, constant-number-of-gradients fashion; combined, these attributes provide sufficient sensitivity for characterizing the underlying distributions in µm-scaled cellular systems. Theoretical derivations and simulations are presented to verify NOGSE's ability to faithfully reconstruct size distributions through suitable modeling of their distribution parameters. Experiments in yeast cell suspensions - where the ground truth can be determined from ancillary microscopy - corroborate these trends experimentally. Finally, by appending to the NOGSE protocol an imaging acquisition, novel MRI maps of cellular size distributions were collected from a mouse brain. The ensuing micro-architectural contrasts successfully delineated distinctive hallmark anatomical sub-structures, in both white matter and gray matter tissues, in a non-invasive manner. Such findings highlight NOGSE's potential for characterizing aberrations in cellular size distributions upon disease, or during normal processes such as development.

Diffusion-assisted selective dynamical recoupling: a new approach to measure background gradients in magnetic resonance.

Dynamical decoupling, a generalization of the original NMR spin-echo sequence, is becoming increasingly relevant as a tool for reducing decoherence in quantum systems. Such sequences apply non-equidistant refocusing pulses for optimizing the coupling between systems, and environmental fluctuations characterized by a given noise spectrum. One such sequence, dubbed Selective Dynamical Recoupling (SDR) [P. E. S. Smith, G. Bensky, G. A. Álvarez, G. Kurizki, and L. Frydman, Proc. Natl. Acad. Sci. 109, 5958 (2012)], allows one to coherently reintroduce diffusion decoherence effects driven by fluctuations arising from restricted molecular diffusion [G. A. Álvarez, N. Shemesh, and L. Frydman, Phys. Rev. Lett. 111, 080404 (2013)]. The fully-refocused, constant-time, and constant-number-of-pulses nature of SDR also allows one to filter out "intrinsic" T1 and T2 weightings, as well as pulse errors acting as additional sources of decoherence. This article explores such features when the fluctuations are now driven by unrestricted molecular diffusion. In particular, we show that diffusion-driven SDR can be exploited to investigate the decoherence arising from the frequency fluctuations imposed by internal gradients. As a result, SDR presents a unique way of probing and characterizing these internal magnetic fields, given an a priori known free diffusion coefficient. This has important implications in studies of structured systems, including porous media and live tissues, where the internal gradients may serve as fingerprints for the system's composition or structure. The principles of this method, along with full analytical solutions for the unrestricted diffusion-driven modulation of the SDR signal, are presented. The potential of this approach is demonstrated with the generation of a novel source of MRI contrast, based on the background gradients active in an ex vivo mouse brain. Additional features and limitations of this new method are discussed.

Measuring small compartment dimensions by probing diffusion dynamics via Non-uniform Oscillating-Gradient Spin-Echo (NOGSE) NMR.

Noninvasive measurements of microstructure in materials, cells, and in biological tissues, constitute a unique capability of gradient-assisted NMR. Diffusion-diffraction MR approaches pioneered by Callaghan demonstrated this ability; Oscillating-Gradient Spin-Echo (OGSE) methodologies tackle the demanding gradient amplitudes required for observing diffraction patterns by utilizing constant-frequency oscillating gradient pairs that probe the diffusion spectrum, D(ω). Here we present a new class of diffusion MR experiments, termed Non-uniform Oscillating-Gradient Spin-Echo (NOGSE), which dynamically probe multiple frequencies of the diffusion spectral density at once, thus affording direct microstructural information on the compartment's dimension. The NOGSE methodology applies N constant-amplitude gradient oscillations; N-1 of these oscillations are spaced by a characteristic time x, followed by a single gradient oscillation characterized by a time y, such that the diffusion dynamics is probed while keeping (N-1)x+y≡TNOGSE constant. These constant-time, fixed-gradient-amplitude, multi-frequency attributes render NOGSE particularly useful for probing small compartment dimensions with relatively weak gradients - alleviating difficulties associated with probing D(ω) frequency-by-frequency or with varying relaxation weightings, as in other diffusion-monitoring experiments. Analytical descriptions of the NOGSE signal are given, and the sequence's ability to extract small compartment sizes with a sensitivity towards length to the sixth power, is demonstrated using a microstructural phantom. Excellent agreement between theory and experiments was evidenced even upon applying weak gradient amplitudes. An MR imaging version of NOGSE was also implemented in ex vivo pig spinal cords and mouse brains, affording maps based on compartment sizes. The effects of size distributions on NOGSE are also briefly analyzed.

Coherent dynamical recoupling of diffusion-driven decoherence in magnetic resonance.

During recent years, dynamical decoupling (DD) has gained relevance as a tool for manipulating and interrogating quantum systems. This is particularly relevant for spins involved in nuclear magnetic resonance (NMR), where DD sequences can be used to prolong quantum coherences, or to selectively couple or decouple the effects imposed by random environmental fluctuations. In this Letter, we show that these concepts can be exploited to selectively recouple diffusion processes in restricted spaces. The ensuing method provides a novel tool to measure restriction lengths in confined systems such as capillaries, pores or cells. The principles of this method for selectively recoupling diffusion-driven decoherence, its standing within the context of diffusion NMR, extensions to the characterization of other kinds of quantum fluctuations, and corroborating experiments, are presented.

Robust dynamical decoupling.

Quantum computers, which process information encoded in quantum mechanical systems, hold the potential to solve some of the hardest computational problems. A substantial obstacle for the further development of quantum computers is the fact that the lifetime of quantum information is usually too short to allow practical computation. A promising method for increasing the lifetime, known as dynamical decoupling (DD), consists of applying a periodic series of inversion pulses to the quantum bits. In the present review, we give an overview of this technique and compare different pulse sequences proposed earlier. We show that pulse imperfections, which are always present in experimental implementations, limit the performance of DD. The loss of coherence due to the accumulation of pulse errors can even exceed the perturbation from the environment. This effect can be largely eliminated by a judicious design of pulses and sequences. The corresponding sequences are largely immune to pulse imperfections and provide an increase of the coherence time of the system by several orders of magnitude.

Controlling spin-spin network dynamics by repeated projective measurements.

We show that coupled-spin network manipulations can be made highly effective by repeated projections of the evolving quantum states onto diagonal density-matrix states (populations). As opposed to the intricately crafted pulse trains that are often used to fine-tune a complex network's evolution, the strategy hereby presented derives from the "quantum Zeno effect" and provides a highly robust route to guide the evolution by destroying all unwanted correlations (coherences). We exploit these effects by showing that a relaxationlike behavior is endowed to polarization transfers occurring within a N-spin coupled network. Experimental implementations yield coupling constant determinations for complex spin-coupling topologies, as demonstrated within the field of liquid-state nuclear magnetic resonance.

Shift-driven modulations of spin-echo signals.

Since the pioneering works of Carr-Purcell and Meiboom-Gill [Carr HY, Purcell EM (1954) Phys Rev 94:630; Meiboom S, Gill D (1985) Rev Sci Instrum 29:688], trains of π-pulses have featured amongst the main tools of quantum control. Echo trains find widespread use in nuclear magnetic resonance spectroscopy (NMR) and imaging (MRI), thanks to their ability to free the evolution of a spin-1/2 from several sources of decoherence. Spin echoes have also been researched in dynamic decoupling scenarios, for prolonging the lifetimes of quantum states or coherences. Inspired by this search we introduce a family of spin-echo sequences, which can still detect site-specific interactions like the chemical shift. This is achieved thanks to the presence of weak environmental fluctuations of common occurrence in high-field NMR--such as homonuclear spin-spin couplings or chemical/biochemical exchanges. Both intuitive and rigorous derivations of the resulting "selective dynamical recoupling" sequences are provided. Applications of these novel experiments are given for a variety of NMR scenarios including determinations of shift effects under inhomogeneities overwhelming individual chemical identities, and model-free characterizations of chemically exchanging partners.

Measuring the spectrum of colored noise by dynamical decoupling.

Decoherence is one of the most important obstacles that must be overcome in quantum information processing. It depends on the qubit-environment coupling strength, but also on the spectral composition of the noise generated by the environment. If the spectral density is known, fighting the effect of decoherence can be made more effective. Applying sequences of inversion pulses to the qubit system, we developed a method for dynamical decoupling noise spectroscopy. We generate effective filter functions that probe the environmental spectral density without requiring assumptions about its shape. Comparing different pulse sequences, we recover the complete spectral density function and distinguish different contributions to the overall decoherence.

Robust dynamical decoupling for quantum computing and quantum memory.

Dynamical decoupling (DD) is a popular technique for protecting qubits from the environment. However, unless special care is taken, experimental errors in the control pulses used in this technique can destroy the quantum information instead of preserving it. Here, we investigate techniques for making DD sequences robust against different types of experimental errors while retaining good decoupling efficiency in a fluctuating environment. We present experimental data from solid-state nuclear spin qubits and introduce a new DD sequence that is suitable for quantum computing and quantum memory.

NMR quantum simulation of localization effects induced by decoherence.

The loss of coherence in quantum mechanical superposition states limits the time for which quantum information remains useful. Similarly, it limits the distance over which quantum information can be transmitted. Here, we investigate in a nuclear spin-based quantum simulator, the localization of the size of spin clusters that are generated by a Hamiltonian driving the transmission of information, while a variable-strength perturbation counteracts the spreading. We find that the system reaches a dynamic equilibrium size, which decreases with the square of the perturbation strength.

Zeno and anti-zeno polarization control of spin ensembles by induced dephasing.

We experimentally and theoretically demonstrate the purity (polarization) control of qubits entangled with multiple spins, using induced dephasing in nuclear magnetic resonance setups to simulate repeated quantum measurements. We show that one may steer the qubit ensemble towards a quasiequilibrium state of a certain purity by choosing suitable time intervals between dephasing operations. These results demonstrate that repeated dephasing at intervals associated with the anti-Zeno regime leads to ensemble purification, whereas those associated with the Zeno regime lead to ensemble mixing.

Quantum parallelism as a tool for ensemble spin dynamics calculations.

Efficient simulations of quantum evolutions of spin-1/2 systems are relevant for ensemble quantum computation as well as in typical NMR experiments. We propose an efficient method to calculate the dynamics of an observable provided that the initial excitation is "local." It resorts to a single entangled pure initial state built as a superposition, with random phases, of the pure elements that compose the mixture. This ensures self-averaging of any observable, drastically reducing the calculation time. The procedure is tested for two representative systems: a spin star (cluster with random long range interactions) and a spin ladder.

Environmentally induced quantum dynamical phase transition in the spin swapping operation.

Quantum information processing relies on coherent quantum dynamics for a precise control of its basic operations. A swapping gate in a two-spin system exchanges the degenerate states |(up arrow, down arrow)> and |(down arrow, up arrow)>. In NMR, this is achieved turning on and off the spin-spin interaction b=DeltaE that splits the energy levels and induces an oscillation with a natural frequency DeltaE/Planck's. Interaction of strength Planck's/tau(SE), with an environment of neighboring spins, degrades this oscillation within a decoherence time scale tau(phi). While the experimental frequency omega and decoherence time tau(phi) were expected to be roughly proportional to b/Planck's and tau(SE), respectively, we present here experiments that show drastic deviations in both omega and tau(phi). By solving the many spin dynamics, we prove that the swapping regime is restricted to DeltaEtau(SE) similar or greater than Planck's. Beyond a critical interaction with the environment the swapping freezes and the decoherence rate drops as 1/tau(phi) proportional to (b/Planck's)2tau(SE). The transition between quantum dynamical phases occurs when omega proportional to sqrt (b/Planck's)2-(k/tau(SE)2 becomes imaginary, resembling an overdamped classical oscillator. Here, 0< or =k2< or =1 depends only on the anisotropy of the system-environment interaction, being 0 for isotropic and 1 for XY interactions. This critical onset of a phase dominated by the quantum Zeno effect opens up new opportunities for controlling quantum dynamics.