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Spin echo

Spin echo is a fundamental phenomenon and pulse sequence in (NMR) and (MRI), first described by Erwin L. Hahn in 1950, in which a refocusing radiofrequency reverses the of spins due to static inhomogeneities, producing a detectable signal at a later time. This technique enables the separation of intrinsic spin-spin relaxation effects (characterized by the time constant T₂) from extrinsic broadening due to field non-uniformities (affecting T₂*), allowing precise measurement of relaxation times and improved signal quality. The basic spin echo sequence begins with a 90° radiofrequency that tips the net into the , where precess at their Larmor frequencies but gradually dephase due to variations. After a time τ, a 180° refocusing inverts the spin phases, causing faster-precessing to catch up with slower ones, resulting in rephasing and a maximum signal—or —at time 2τ. The decays exponentially as S = S_0 \exp(-2\tau / T_2), reflecting true transverse relaxation without instrumental artifacts. Hahn's original experiments on liquids demonstrated this constructive of precessing moments, also revealing effects like spin diffusion that influence . In NMR spectroscopy, spin echo sequences are essential for high-resolution studies, refocusing evolution and J-couplings in multidimensional experiments, while in MRI, they form the basis for T1-, -, and proton density-weighted by controlling repetition time () and echo time (). Spin echo MRI provides robust contrast for detecting , such as or tumors, and is less susceptible to from differences compared to methods, though it requires longer acquisition times. Extensions like fast spin echo (with multiple 180° pulses per excitation) enhance efficiency for clinical applications across various field strengths.

History

Discovery and Early Experiments

The spin echo phenomenon was first discovered by Erwin L. Hahn in 1950 while conducting experiments on (NMR) using (RF) techniques. Hahn applied intense RF power in the form of short pulses to an ensemble of spins in a sample placed within a large static , observing unexpected signals that reappeared after initial . These signals, termed spin echoes, emerged as spontaneous nuclear induction responses due to the constructive interference of precessing macroscopic moment vectors following multiple RF pulses. In Hahn's foundational setup, the sample consisted of liquids such as glycerine or doped with ferric nitrate ((NO₃)₃) to shorten relaxation times, enabling clearer of transient effects. The experiment utilized a static of approximately 0.4 T (around 4000 gauss), with RF tuned to the proton Larmor frequency near 17 MHz. The sequence involved a initial 90° RF to tip the spins into the , followed by a delay τ, then a 180° refocusing , and another delay τ, at which point the echo signal was detected as a refocused transverse magnetization peaking at time 2τ after the first . This refocused signal appeared after the spins had dephased due to local variations in the , demonstrating a reversible loss of coherence rather than permanent decay. Hahn's initial theoretical interpretation framed the echo as a refocusing of caused primarily by static inhomogeneities, distinct from irreversible relaxation processes. Drawing on Bloch's phenomenological equations, he explained how the 180° pulse reversed the evolution of , allowing those experiencing faster or slower to realign and produce a measurable . This insight highlighted the 's utility in distinguishing reversible from true spin-spin relaxation. Hahn detailed these findings in his seminal paper "Spin Echoes," published in Physical Review in November 1950 (Vol. 80, pp. 580–594), which laid the groundwork for pulsed NMR techniques. The work marked a pivotal shift from continuous-wave to pulsed methods in NMR experimentation. Following the foundational work in nuclear magnetic resonance (NMR) by Erwin Hahn in 1950, spin echo techniques saw significant interdisciplinary expansions in the ensuing decades. In 1954, Herman Carr and Edward Purcell developed a multiple-echo sequence using a series of 180° pulses after an initial 90° pulse, which was later refined by Solomon Meiboom and Gill in 1958 to correct phase errors; known as the Carr-Purcell-Meiboom-Gill (CPMG) sequence, it allowed for more accurate T₂ measurements by reducing the effects of spin diffusion and field inhomogeneities. In the 1970s, these methods were adapted for magnetic resonance imaging (MRI), with Raymond Damadian and collaborators constructing the first whole-body scanner, Indomitable, which employed spin echo sequences to produce the inaugural human scan in 1977, demonstrating differential relaxation times in tissues for diagnostic purposes. A major milestone occurred in 1972 when Ferenc Mezei invented neutron spin echo (NSE) spectroscopy, leveraging polarized s and magnetic fields to achieve sub-neutron-velocity resolution for probing slow atomic and in materials, such as chain motions and magnetic fluctuations, far surpassing conventional inelastic . This technique, first demonstrated at the Neutron Centre, enabled energy resolutions down to 10^{-9} eV, opening avenues in and . During the 1980s and 1990s, spin echo principles extended to (EPR), where pulsed techniques like electron spin echo envelope modulation (ESEEM) and two-dimensional electron spin echo (ESE) spectroscopy advanced the study of paramagnetic centers in biological and chemical systems, allowing distance measurements between spins with precision. Concurrently, optical echoes emerged as a counterpart in , with intensive developments enabling ultrafast all-optical signal processing and coherent control of molecular excitations in condensed phases, as explored in rare-earth doped crystals for potential applications. More recently, in , studies revealed periodic spin echoes—manifesting as echo trains—in through strong spin-resonator coupling, as observed in ensembles of donor spins in coupled to cavities, where vacuum Rabi splitting facilitated multiple refocusing pulses without external driving, enhancing times for quantum sensing and . These advancements underscore the enduring versatility of spin echo across , , and quantum technologies.

Principles of Operation

Dephasing and Refocusing

In (NMR), spin dephasing refers to the loss of in the transverse magnetization of an ensemble of , which arises primarily from two mechanisms: static inhomogeneities and dynamic spin-spin interactions. Static inhomogeneities, such as variations in the external B_0 across the sample (typically on the order of 1 ), cause at different locations to precess at slightly different Larmor frequencies, leading to a fanning out of the magnetization vectors in the transverse plane over time. Dynamic , in contrast, stems from fluctuating local generated by interactions between , such as dipole-dipole couplings, which introduce random phase shifts that are inherently irreversible. This process is quantified in terms of transverse relaxation, where the observed relaxation time T_2^* represents the effective decay of transverse and includes both reversible (static) and irreversible (dynamic) components, resulting in T_2^* < T_2. The true spin-spin relaxation time T_2, however, isolates the irreversible dynamic effects, excluding the reversible contributions from static inhomogeneities that can be compensated. In the Hahn spin echo experiment, this distinction was pivotal, as the technique demonstrated that static could be undone, revealing the underlying T_2 process. Refocusing of dephasing is achieved through the application of a 180° radiofrequency pulse, which inverts the phases of the transverse magnetization vectors, effectively reversing their dephasing trajectories for static inhomogeneities. In the vector model of magnetization, following an initial excitation that places the net magnetization in the transverse plane, individual spin vectors precess at their respective frequencies due to local field variations, causing the ensemble to spread and the net signal to diminish. The 180° pulse acts like a mirror reflection in the rotating frame, flipping the positions of the vectors such that those precessing faster (due to higher local fields) now trail behind and catch up to the slower ones during an equal subsequent evolution period, leading to rephasing and reformation of the echo signal. This refocusing specifically recovers signal lost to reversible T_2^* effects but cannot compensate for the intrinsic T_2 decay from spin-spin interactions.

Hahn Spin Echo Sequence

The Hahn spin echo sequence is a fundamental pulse protocol in nuclear magnetic resonance (NMR) that generates a refocused signal through a two-pulse radiofrequency (RF) excitation scheme. It begins with a 90° RF pulse that rotates the net magnetization from the longitudinal (z) axis into the transverse (xy) plane, initiating free precession of the spins and producing a free induction decay (FID) signal. After an interval τ, a 180° refocusing RF pulse is applied, which inverts the phases of the spins, reversing their dephasing due to static field inhomogeneities and allowing rephasing to occur. The resulting spin echo signal peaks at time 2τ following the initial 90° pulse, forming a symmetric echo centered around this maximum. The echo time (TE) is defined by the relation TE = 2\tau, where τ represents the time interval between the 90° and 180° pulses, ensuring the echo formation precisely at twice this delay due to the symmetric refocusing mechanism. This timing allows the sequence to effectively compensate for constant field offsets, producing a detectable transverse magnetization that decays primarily due to intrinsic spin-spin interactions rather than external inhomogeneities. In practical implementations, particularly in magnetic resonance imaging (MRI), the RF pulses must possess sufficient bandwidth to excite the desired frequency range while minimizing off-resonance effects. Slice selection is achieved by applying a linear magnetic field gradient along the desired imaging plane during both the 90° and 180° pulses, which spatially encodes the excitation such that only spins within a specific thickness resonate at the RF frequency; the slice thickness is inversely proportional to the product of the gradient strength and RF bandwidth. This enables volumetric imaging while maintaining the core refocusing properties of the .

Relaxation and Signal Decay

Spin-Echo Decay

In the spin echo sequence, the amplitude of the refocused magnetization signal diminishes over time due to irreversible spin-spin interactions, a process governed by the transverse relaxation time constant T_2. This decay is exponential, described by the equation A(TE) = A_0 e^{-TE / T_2}, where A(TE) is the echo amplitude at echo time TE, A_0 is the initial transverse magnetization amplitude immediately after the excitation pulse, and T_2 quantifies the rate of this irreversible dephasing. To measure T_2, the interval \tau between the 90° excitation pulse and the 180° refocusing pulse is systematically varied, which doubles to set TE = 2\tau; the resulting amplitudes are then plotted as \ln(A) versus TE, yielding a straight line whose slope is -1/T_2. The primary factors driving this decay include dipole-dipole interactions between spins, modulated by random molecular tumbling in solution, and chemical exchange processes that randomize spin phases across different molecular environments; notably, the sequence refocuses reversible dephasing from static magnetic field inhomogeneities. For instance, in pure water at room temperature, T_2 values range from approximately 2 to 3 seconds, reflecting minimal interactions, while in human soft tissues such as brain gray or white matter during clinical at 1.5 T, T_2 typically falls in the 70–100 ms range due to increased molecular complexity and interactions.

T2 Relaxation vs. T2* Effects

In nuclear magnetic resonance (NMR), T₂ relaxation represents the intrinsic spin-spin relaxation process, arising from random fluctuations in local magnetic fields due to molecular interactions and motions that cause irreversible dephasing of transverse magnetization. These fluctuations lead to a gradual loss of phase coherence among spins, with the transverse magnetization decaying exponentially as M_xy(t) = M_0 exp(-t/T₂), where T₂ is the time constant for this decay to reach 1/e of its initial value. In contrast, T₂* relaxation describes the observed transverse decay in the presence of both T₂ effects and additional reversible dephasing caused by static magnetic field inhomogeneities, such as those from imperfect shimming, sample susceptibility variations, or chemical shift differences. This results in a faster overall decay, quantified by the relation 1/T₂* = 1/T₂ + 1/T₂_inh, where T₂_inh is the dephasing time constant due to these static gradients, making T₂* ≤ T₂. The static inhomogeneities cause spins in different spatial locations to precess at slightly different frequencies, leading to rapid fanning out of the magnetization vector without the irreversible mixing inherent to T₂ processes. The spin echo technique, introduced by Hahn, mitigates the reversible component of T₂* by applying a 180° refocusing pulse that reverses the phase accrual from static field gradients, allowing the echo signal to decay primarily according to the true T₂ relaxation time rather than the faster T₂*. This refocusing occurs at an echo time TE = 2τ, where τ is the interval from the initial excitation to the 180° pulse, effectively canceling dephasing from constant field offsets while irreversible T₂ effects continue unabated. Experimentally, this distinction is evident when comparing the free induction decay (FID) signal, which decays with T₂* due to unmitigated inhomogeneities, to the spin echo signal at the same TE, which exhibits a slower decay governed by T₂ alone, highlighting the refocusing of static dephasing effects.

Echo Variants

Stimulated Echo

The stimulated echo is produced in nuclear magnetic resonance (NMR) using a three-pulse sequence consisting of 90° radiofrequency (RF) pulses applied at specific intervals: the first 90° pulse, followed by a delay τ, the second 90° pulse, a mixing time TM, the third 90° pulse, and another delay τ during which the echo forms. This configuration, first described in the context of spin echo phenomena, enables the formation of an echo that combines elements of both transverse and longitudinal relaxation processes. In the mechanism of the stimulated echo, the initial 90° pulse rotates the equilibrium longitudinal magnetization into the transverse plane, where it dephases due to magnetic field inhomogeneities and T₂ relaxation effects over the interval τ. The subsequent second 90° pulse then redirects this dephased transverse magnetization along the longitudinal axis, storing it as longitudinal magnetization during the mixing time TM, during which it recovers according to T₁ relaxation. The third 90° pulse rotates this stored longitudinal component back into the transverse plane, allowing the spins to rephase and produce the stimulated echo after an additional interval τ, effectively refocusing the dephasing that occurred before the storage period. This longitudinal storage distinguishes the stimulated echo from simpler two-pulse spin echoes, as it decouples the dephasing and refocusing intervals. A key advantage of the stimulated echo sequence is its ability to probe longer effective evolution times for processes like diffusion without being fully limited by the shorter T₂ relaxation time, since the magnetization stored longitudinally during TM decays primarily via the longer T₁ relaxation. The amplitude of the stimulated echo, neglecting diffusion, is given by M_{\text{STE}} = M_0 \exp\left(-\frac{2\tau}{T_2}\right) \exp\left(-\frac{TM}{T_1}\right), where M_0 is the initial magnetization, reflecting T₂ decay during the two transverse intervals of length τ each and T₁ decay during the mixing time TM. This property makes the sequence particularly valuable for applications such as measuring self-diffusion coefficients in viscous samples or studying partial refocusing in T₁/T₂ contrast studies, where extended observation times are beneficial.

Photon Echo

Photon echo is the optical counterpart to the spin echo phenomenon, applying similar refocusing principles to coherent excitations in two-level atomic or molecular systems at optical frequencies rather than magnetic spins. Short, intense laser pulses replace radiofrequency excitations, creating transient coherences in ensembles of atoms or molecules, such as in dilute gases or solid-state materials like crystals. This adaptation enables the study of dephasing mechanisms in optical transitions, where inhomogeneous broadening dominates the linewidth. The pulse sequence analogy mirrors the spin echo but uses two π/2 laser pulses separated by a delay τ. The first pulse induces a macroscopic polarization by coherently exciting the two-level systems, after which the coherence dephases due to mechanisms like Doppler shifts from atomic motion in gases or inhomogeneous broadening from local environmental variations in solids. The second π/2 pulse inverts the phase accumulation, reversing the dephasing process and causing the dipoles to rephase, resulting in the emission of a coherent light pulse—the photon echo—at time 2τ. This refocusing isolates the homogeneous dephasing component, providing insight into intrinsic relaxation processes. The phenomenon was first observed in the mid-1960s in ruby crystals, where two laser pulses exciting the chromium-ion R1 optical transition produced a delayed echo signal, demonstrating the reversibility of optical coherence. The echo intensity follows an exponential decay given by I \propto \exp(-2\tau / T_2), similar to the NMR spin echo but with T_2 denoting the optical transverse relaxation time, which captures pure dephasing and population decay effects in the excited state. In contrast to NMR spin echoes, photon echoes require no external static magnetic field to establish a reference frequency, as they rely directly on the electronic transition energy. The echo manifests as a sharp peak in the intensity of spontaneously emitted light, propagating in a phase-matched direction distinct from the excitation beams, allowing spatial separation from scattered light.

Fast Spin Echo

Fast spin echo (FSE), also known as turbo spin echo or rapid acquisition with relaxation enhancement (RARE), is a multi-echo variant of the spin echo sequence that enables rapid data acquisition in magnetic resonance imaging (MRI) by generating multiple echoes per excitation. The sequence starts with a 90° radiofrequency excitation pulse, followed by a series of 180° refocusing pulses that produce a train of 8–16 spin echoes within a single repetition time (TR). Each echo in the train is encoded with a unique phase-encoding gradient, allowing different lines of k-space to be filled efficiently and reconstructing the image via Fourier transform. This approach extends the basic Hahn spin echo sequence by applying multiple refocusing pulses to refocus dephasing spins repeatedly within one TR. Introduced by Hennig et al. in 1986, FSE was developed to address the long scan times of conventional spin echo methods and became a standard clinical technique in the 1990s with advancements in gradient hardware and pulse sequence design. A primary benefit of FSE is the substantial reduction in acquisition time, as multiple k-space lines are acquired per TR; for instance, it can complete a 256 × 256 resolution image in 2–40 seconds, compared to minutes for single-echo sequences. This efficiency fills k-space segments across echoes with varied phase encoding, enabling faster coverage of anatomical regions while maintaining spin echo contrast. Despite these advantages, FSE introduces T₂ blurring in the phase-encoding direction because later echoes in the train experience greater T₂ decay due to their longer echo times, attenuating high spatial frequency components. Image contrast is controlled by selecting the effective echo time (eff), defined as the echo time corresponding to the center of the echo train (or low frequencies), approximated as \text{TE}_\text{eff} = \text{TE}_1 + \left\lfloor \frac{N}{2} \right\rfloor \times \text{ESP}, where TE1 is the first echo time, N is the echo train length, and ESP is the inter-echo spacing.

Applications and Advanced Techniques

In NMR Spectroscopy and MRI

In (NMR) spectroscopy, spin echo techniques are essential for enhancing and enabling precise by refocusing dephasing caused by inhomogeneities. The Hahn spin echo , consisting of a 90° followed by a 180° refocusing , forms the basis for high-resolution NMR experiments, allowing the isolation of true spin-spin relaxation times (T₂) without interference from T₂* effects. This refocusing mechanism is particularly valuable in one-dimensional (1D) and two-dimensional () experiments, where spin echoes facilitate spectral editing to suppress unwanted signals, such as those from solvents or broad resonances, thereby improving the visibility of molecular features in complex mixtures. For instance, in protein NMR, spin echo pulses are integrated into schemes to eliminate heteronuclear artifacts, yielding cleaner spectra for assignment of chemical shifts and coupling constants. A key application is the Carr-Purcell-Meiboom-Gill (CPMG) , an extension of the Hahn that employs a train of 180° pulses to generate multiple echoes, enabling accurate T₂ measurements in solution-state NMR. This method is widely used for characterizing and conformational changes, as the echo train refocuses inhomogeneous broadening while the signal decay reflects intrinsic relaxation processes. In and biochemical studies, CPMG is applied to edit spectra by attenuating broad macromolecular signals, allowing focused analysis of small metabolites with relaxation filtering. Quantitative T₂ data from CPMG experiments provide insights into binding interactions or aggregation states, with typical T₂ values ranging from milliseconds in viscous samples to seconds in dilute solutions, aiding structural elucidation without extensive computational modeling. In magnetic resonance imaging (MRI), spin echo sequences are cornerstone methods for T₂-weighted imaging, which exploit transverse relaxation differences to generate tissue contrast while mitigating artifacts from static magnetic field inhomogeneities. The 90°-180° pulse pair refocuses dephasing due to susceptibility variations, such as those near air-tissue interfaces, producing images where cerebrospinal fluid (CSF) appears bright owing to its long T₂ (approximately 2000 ms), while fat shows intermediate intensity (T₂ around 80 ms) and muscle is darker (T₂ about 50 ms). This contrast mechanism is critical for detecting edema, inflammation, or tumors, as pathological tissues often exhibit prolonged T₂ compared to healthy counterparts. Conventional spin echo remains a standard for initial diagnostic scans, providing robust suppression of field distortions in regions like the brain. Fast spin echo (FSE), also known as turbo spin echo, accelerates acquisition by filling multiple k-space lines per excitation using an echo train, reducing scan times from minutes to seconds without significant loss in T₂ contrast. Recent advancements as of 2025 incorporate artificial intelligence (AI) to further accelerate FSE sequences, improving image quality in T₂-weighted brain MRI while reducing acquisition times. In clinical protocols, FSE is routinely employed for brain imaging to evaluate white matter lesions or stroke, where echo trains of 8-16 pulses yield high-resolution T₂-weighted images with minimal blurring. For knee MRI, FSE sequences with fat suppression highlight meniscal tears or cartilage defects, leveraging the technique's efficiency to cover the joint in under 5 minutes per plane. Spin echo-based T₂ mapping, acquired via multi-echo trains, quantifies relaxation times pixel-by-pixel, enabling early pathology detection; for example, elevated T₂ values (e.g., >100 ms in normal-appearing tissue) signal occult inflammation in multiple sclerosis or myocarditis, guiding therapeutic decisions.

Modern Variants and Emerging Uses

Modern variants of spin echo techniques have evolved to address limitations in speed, , and applicability, particularly in that integrate refocusing for enhanced . The and Spin Echo (GRASE) combines multiple Hahn spin echoes with short trains of echoes to achieve rapid T2-weighted multisection while preserving the contrast and resolution of conventional spin echo methods. This approach reduces acquisition times dramatically, enabling 11 body sections in 18 seconds or 22 brain sections in 36 seconds, compared to over 12 minutes for standard spin echo, and minimizes artifacts like respiratory motion in abdominal during brief breath-holds. In contemporary applications, such as myocardial T2 mapping at 1.5 Tesla, an optimized GRASE with six echoes and dual inversion allows single-breath-hold per slice in under 13 seconds, offering high reliability with inter-study variability of -0.02 ms and excellent observer agreement. This facilitates quantitative tissue characterization, detecting elevated T2 relaxation times (e.g., 61.3 ms in acute injury vs. 52.2 ms in healthy tissue), which supports clinical diagnosis of myocardial conditions. Multi-echo spin echo sequences have also advanced diffusion-weighted (DWI) by generating echo trains through repeated 180° refocusing pulses, mitigating susceptibility-induced distortions and T2* blurring inherent in gradient-echo alternatives. The diffusion-weighted spin-echo echo-planar (DW-SE-EPI) sequence, a of modern DWI, pairs a spin echo preparation with single-shot echo-planar readout to encode while maintaining high (SNR) and reducing artifacts. This enables robust microstructural assessment in clinical settings, such as tumor or detection, with improved spatial fidelity over non-spin-echo methods. Variants like twice-refocused spin echo (TRSE) further enhance performance by splitting diffusion gradients into shorter pulses for better , often integrated with balanced steady-state free to yield higher-resolution images with minimal geometric distortion. Integration of spin echo with (DNP) has revolutionized metabolic imaging by amplifying nuclear signals for real-time visualization of biomolecular processes. In hyperpolarized 13C MRI, double spin-echo sequences employing low flip angles preserve the transient hyperpolarization during echo-planar sampling, enabling rapid spectroscopic imaging of metabolites like pyruvate with over 50,000-fold SNR enhancement over thermal . This approach supports dynamic assessment of metabolic fluxes , such as in , where it distinguishes tumor rates noninvasively. Fast spin-echo variants, akin to turbo spin-echo, further accelerate acquisition in DNP-enhanced studies, reducing T2 decay effects and allowing multi-slice coverage for whole-organ metabolic mapping. In quantum technologies, spin echoes extend coherence times in nitrogen-vacancy (NV) centers within , serving as quantum sensors and memories. By applying π pulses to refocus from spin baths, Hahn echoes achieve ultra-long coherence up to 2.4 ms at , enabling high-fidelity manipulation for nanoscale magnetometry. Recent advancements, including dynamical decoupling protocols, push NV spin coherence beyond 10 seconds under zero , enhancing sensing resolution for near-surface fields. For qubits, spin echoes underpin error suppression in and -based systems; three-qubit phase-correcting codes using NV-associated spins maintain above 74% against bit- and phase-flips, with coherence extended to 1.9 minutes for paired spins via optimized waveforms. Emerging 2020s studies leverage resonator-coupled spin echoes for ultrasensitive quantum sensing, where microwave resonators amplify faint echo signals from spin ensembles. Techniques like detectors enable in situ amplification of zeptojoule-level echoes, achieving 500-fold signal enhancement for detecting paramagnetic defects or weak fields without cryogenic cooling. This resonator-mediated detection, often via readout, supports coherent spin dynamics measurement in solids, advancing hybrid quantum devices for . Looking ahead, spin echo techniques hold promise in portable NMR devices, where turbo spin-echo adaptations enable high-throughput imaging in compact, low-field systems. As of 2025, advancements in low-field MRI have enhanced spin echo sequences for portable diagnostics, improving accessibility in resource-limited settings with better signal quality and reduced power needs. Parallelized turbo spin-echo scans in unilateral NMR setups accelerate relaxation mapping by factors up to 18, producing multi-echo images of multiple samples with sub-ppm homogeneity, ideal for on-site chemical analysis. In , spin-echo-based dynamical decoupling forms the basis for error correction, suppressing decoherence in spin qubits to approach fault-tolerant thresholds, as demonstrated in arrays with phase-flip protection exceeding uncorrected baselines by orders of magnitude. These developments position spin echoes as enablers for scalable, field-deployable quantum technologies and precision diagnostics.

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