Double spin-echo sequence for rapid spectroscopic imaging of hyperpolarized 13C

Dynamic nuclear polarization of metabolically active compounds labeled with (13)C has been introduced as a means for imaging metabolic processes in vivo. To differentiate between the injected compound and the various metabolic products, an imaging technique capable of separating the different chemical-shift species must be used. In this paper, the design and testing of a pulse sequence for rapid magnetic resonance spectroscopic imaging (MRSI) of hyperpolarized (13)C is presented. The pulse sequence consists of a small-tip excitation followed by a double spin echo using adiabatic refocusing pulses and a "flyback" echo-planar readout gradient. Key elements of the sequence are insensitivity to calibration of the transmit gain, the formation of a spin echo giving high-quality spectral information, and a small effective tip angle that preserves the magnetization for a sufficient duration. Experiments in vivo showed three-dimensional coverage with excellent spectral quality and SNR.     

Frequency-specific SSFP for hyperpolarized C metabolic imaging at 14.1 T

Metabolic imaging of hyperpolarized [1-¹³C] pyruvate co-polarized with [¹³C]urea by dynamic nuclear polarization with rapid dissolution is a promising new method for assessing tumor metabolism and perfusion simultaneously in vivo. Novel pulse sequences are required to enable dynamic imaging of multiple ¹³C spectral lines with high spatiotemporal resolution. The goal of this study was to investigate a new frequency-specific approach for rapid metabolic imaging of multiple ¹³C resonances using the spectral selectivity of steady-state free precession pulse (SSFP) trains. Methods developed in simulations were implemented in a dynamic frequency-cycled balanced SSFP pulse sequence on a 14.1-T animal magnetic resonance imaging scanner. This acquisition was tested in thermal and hyperpolarized phantom imaging studies and in a transgenic mouse with prostate cancer.     

Investigating hyperpolarized Xe and CPMAS for spin polarization transfer to surface nuclei: a model study

Several experimental techniques have been developed to utilize spin-polarized xenon gas for sensitivity and selectivity enhancement in surface studies using solid-state NMR. Although previously reported as a viable spin polarization transfer mechanism, the details of high-field cross-polarization (CP) have not been thoroughly investigated. We recently reported observations of CP from an adsorbed layer of hyperpolarized xenon (HP Xe) to a variety of surface nuclei at temperatures as high as 323 K [J. Am. Chem. Soc. 105 (2001) 1412]. In this paper, we investigate many of the issues associated with HP Xe surface CP studies, including polarization transfer kinetics and the effects of temperature on the dynamics. Protonated and methylated silica samples are used as model systems for comparison. A comparison of the rate analysis data from CP and SPINOE (Spin Polarization-Induced Nuclear Overhauser Effect) experiments provides information on the origin of the difference in polarization transfer efficiencies between the two techniques. Lineshape analysis of ¹H spectra for CP and SPINOE experiments demonstrates the difference in selectivity of methods due to longer SPINOE evolution times that lead to greater spin diffusion. The results of this work help to assess the viability of HP Xe CP as a surface analysis technique.     

Investigating tumor perfusion and metabolism using multiple hyperpolarized (13)C compounds: HP001, pyruvate and urea

The metabolically inactive hyperpolarized agents HP001 (bis-1,1-(hydroxymethyl)-[1-(13)C]cyclopropane-d(8)) and urea enable a new type of perfusion magnetic resonance imaging based on a direct signal source that is background-free. The addition of perfusion information to metabolic information obtained by spectroscopic imaging of hyperpolarized [1-(13)C]pyruvate would be of great value in exploring the relationship between perfusion and metabolism in cancer. In preclinical normal murine and cancer model studies, we performed both dynamic multislice imaging of the specialized hyperpolarized perfusion compound HP001 (T(1)=95 s ex vivo, 32 s in vivo at 3 T) using a pulse sequence with balanced steady-state free precession and ramped flip angle over time for efficient utilization of the hyperpolarized magnetization and three-dimensional echo-planar spectroscopic imaging of urea copolarized with [1-(13)C]pyruvate, with compressed sensing for resolution enhancement. For the dynamic data, peak signal maps and blood flow maps derived from perfusion modeling were generated. The spatial heterogeneity of perfusion was increased 2.9-fold in tumor tissues (P=.05), and slower washout was observed in the dynamic data. The results of separate dynamic HP001 imaging and copolarized pyruvate/urea imaging were compared. A strong and significant correlation (R=0.73, P=.02) detected between the urea and HP001 data confirmed the value of copolarizing urea with pyruvate for simultaneous assessment of perfusion and metabolism.     

Design of spectral-spatial outer volume suppression RF pulses for tissue specific metabolic characterization with hyperpolarized C pyruvate

[1-¹³C] pyruvate pre-polarized via DNP has been used in animal models to probe changes in metabolic enzyme activities in vivo. To more accurately assess the metabolic state and its change from disease progression or therapy in a specific region or tissue in vivo, it may be desirable to separate the downstream ¹³C metabolite signals resulting from the metabolic activity within the tissue of interest and those brought into the tissue by perfusion. In this study, a spectral-spatial saturation pulse that selectively saturates the signal from the metabolic products [1-¹³C] lactate and [1-¹³C] alanine was designed and implemented as outer volume suppression for localized MRSI acquisition. Preliminary in vivo results showed that the suppression pulse did not prevent the pre-polarized pyruvate from being delivered throughout the animal while it saturated the metabolites within the targeted saturation region.     

On the effects of dephasing due to local gradients in diffusion tensor imaging experiments: relevance for diffusion tensor imaging fiber phantoms

The effect of susceptibility differences between fluid and fibers on the properties of DTI fiber phantoms was investigated. Thereto, machine-made, easily producible and inexpensive DTI fiber phantoms were constructed by winding polyamide fibers of 15 microm diameter around a circular acrylic glass spindle. The achieved fractional anisotropy was 0.78+/-0.02. It is shown by phantom measurements and Monte Carlo simulations that the transversal relaxation time T(2) strongly depends on the angle between the fibers and the B(0) field if the susceptibilities of the fibers and fluid are not identical. In the phantoms, the measured T(2) time at 3 T decreased by 60% for fibers running perpendicular to B(0). Monte Carlo simulations confirmed this result and revealed that the exact relaxation time depends strongly on the exact packing of the fibers. In the phantoms, the measured diffusion was independent of fiber orientation. Monte Carlo simulations revealed that the measured diffusion strongly depends on the exact fiber packing and that field strength and -orientation dependencies of measured diffusion may be minimal for hexagonal packing while the diffusion can be underestimated by more than 50% for cubic packing at 3 T. To overcome these effects, the susceptibilities of fibers and fluid were matched using an aqueous sodium chloride solution (83 g NaCl per kilogram of water). This enables an orientation independent and reliable use of DTI phantoms for evaluation purposes.     

An open-access, very-low-field MRI system for posture-dependent 3He human lung imaging

We describe the design and operation of an open-access, very-low-field, magnetic resonance imaging (MRI) system for in vivo hyperpolarized ³He imaging of the human lungs. This system permits the study of lung function in both horizontal and upright postures, a capability with important implications in pulmonary physiology and clinical medicine, including asthma and obesity. The imager uses a bi-planar B₀ coil design that produces an optimized 65 G (6.5 mT) magnetic field for ³He MRI at 210 kHz. Three sets of bi-planar coils produce the x, y, and z magnetic field gradients while providing a 79-cm inter-coil gap for the imaging subject. We use solenoidal Q-spoiled RF coils for operation at low frequencies, and are able to exploit insignificant sample loading to allow for pre-tuning/matching schemes and for accurate pre-calibration of flip angles. We obtain sufficient SNR to acquire 2D ³He images with up to 2.8 mm resolution, and present initial 2D and 3D ³He images of human lungs in both supine and upright orientations. ¹H MRI can also be performed for diagnostic and calibration reasons.     

Mechanism of sonochemical reduction of permanganate to manganese dioxide in aqueous alcohol solutions: Reactivities of reducing species formed by alcohol sonolysis

The sonochemical reduction of MnO₄⁻ to MnO₂ in aqueous solutions was investigated as a function of alcohol concentration under Ar. The rate of MnO₄⁻ reduction initially decreased with increasing alcohol concentration, and then increased when the alcohol concentration was increased further. The concentrations at which the reduction rates were minimum depended on the hydrophobic properties of the added alcohols under ultrasonic irradiation. At low concentrations, the alcohols acted as OH radical scavengers; at high concentrations, they acted as reductant precursors: R_ab, formed by abstraction reactions of the alcohols with sonochemically formed OH radicals or H atoms, and R_py, formed by alcohol pyrolysis under ultrasonic irradiation. The results suggest that the reactivity order of the sonochemically formed reducing species with MnO₄⁻ at pH 7–9 is the sum of H₂O₂ and H > R_py > R_ab. The peak wavelengths of MnO₂ colloidal solutions formed at high 1-butanol concentrations shifted to shorter wavelengths, suggesting the formation of small particles at high 1-butanol concentrations. The rates of sonochemical reduction of MnO₂ to Mn²⁺ in the presence of 1-butanol were slower than that in the absence of 1-butanol, because the sonochemical formation of H₂O₂ and H, which act as reductants, was suppressed by 1-butanol in aqueous solutions.     

Use of capillaries in the construction of an MRI phantom for the assessment of diffusion tensor imaging: demonstration of performance

Although diffusion tensor imaging (DTI) shows great potential for the diagnosis of a variety of pathologies, no consensus for an appropriate assessment standard of DTI exists. This study examined the feasibility of using water-filled arrays of glass capillaries to construct a DTI phantom suitable for making repeated and reproducible measurements required in a quality assessment program. Three phantoms were constructed using arrays of capillaries with three inner diameters (23, 48, and 82 μm). Data were acquired using DTI protocols; the fractional anisotropy (FA), mean apparent diffusion coefficient (ADC) and principal eigenvectors of the diffusion tensors were calculated. This study demonstrated four results: (1) echo-planar images show that susceptibility within the capillary arrays does not lead to substantial differences in precessional frequency in regions containing the arrays and neither do the regions show noticeable image distortion; (2) principal eigenvectors of the diffusion tensors agree to within <10.3° of the array orientations; (3) mean FA values (0.18–0.50) and ADC values (1.40–1.93×10−³ mm²/s) within specified regions of interest are in general agreement with simulations after a simple noise correction; and (4) these array performance characteristics are observable using a typical clinical DTI protocol.     

Response of Mn overlayers on Fe to external magnetic fields: Electronic structure calculations

The behavior of Mn overlayers on Fe(0 0 1) under the influence of external magnetic fields is investigated. The electronic charge distribution, local magnetic moments as well as their couplings are determined as a function of the external field by solving self-consistently a tight binding Hamiltonian, parameterized to ab initio TBLMTO calculations. Our method allows to trace back the field-dependent average magnetization of the system to its electronic structure and magnetic configuration. We show how in the non-collinear framework the response of the system is markedly different to what is found in the collinear framework. If metastable magnetic configurations exist, the external field can be used for tuning the system between some of them because the system stays in some of those metastable states even after switching off the external field.     

Non-convex algorithm for sparse and low-rank recovery: Application to dynamic MRI reconstruction

In this work we exploit two assumed properties of dynamic MRI in order to reconstruct the images from under-sampled K-space samples. The first property assumes the signal is sparse in the x-f space and the second property assumes the signal is rank-deficient in the x-t space. These assumptions lead to an optimization problem that requires minimizing a combined l_p-norm and Schatten-p norm. We propose a novel FOCUSS based approach to solve the optimization problem. Our proposed method is compared with state-of-the-art techniques in dynamic MRI reconstruction. Experimental evaluation carried out on three real datasets shows that for all these datasets, our method yields better reconstruction both in quantitative and qualitative evaluation.     

Application of the semivariogram to MRI data: a useful approach for the characterization of natural porous rocks

Geostatistics is used to study the heterogeneities of reservoir cores, as well as to observe the orientation of layers inside the cores. This information obtained from geostatistics could be very useful for coreflood simulation programs. In this paper, it has been shown how semivariograms can be drawn using local porosities obtained from magnetic resonance imaging (MRI). These semivariograms are then used to determine the correlation lengths of the porosity in the cores and to qualitatively estimate the degree of heterogeneity in the core samples.     

基于光梳的腔增强傅里叶变换光谱：在碰撞线形研究中的应用

本文在近红外区域构造了基于光学频率梳的腔增强傅里叶变换光谱仪,并用于Ar干扰的CO振转跃迁的谱线研究,高灵敏度的测量波数从6270 cm^-1到6410 cm^-1,涵盖CO第二泛频带的P和R分支. 该光谱仪提供的高分辨率超过了由干涉图长度确定的傅立叶变换分辨率极限,成功消除了线型函数的振铃和展宽效应. 本文可观察到Voigt线型曲线外的碰撞效应. 通过拟合速度依赖的Voigt曲线重新得到碰撞线型曲线参数,并与使用基于光学频率梳的高精密连续激光光腔衰荡光谱测量结果非常吻合.     

Modeling ferrocene reactions and iron nanoparticle formation: Application to CVD synthesis of carbon nanotubes

This paper presents a practically useful model that can predict the formation process and the growth rate of iron nanoparticles from ferrocene. There is a strong need to create such a model that can help improve the process of carbon nanotube (CNT) production by chemical vapor deposition (CVD) and flame synthesis methods. This study serves this purpose. A simple reaction mechanism between ferrocene and hydrogen was proposed based on experimental and theoretical studies conducted by other researchers; then the method of moments with interpolative closure (MOMIC) was applied to compute the size distribution of iron particles. MOMIC was found to reproduce the result of a sectional method with better accuracy than a lognormal method. We simulated the isothermal decomposition of ferrocene and the consequent formation of iron particles with MOMIC; the computed diameter of iron particles agreed reasonably well with experimental data. Analytical solutions for particle diameter were obtained as a function of residence time, assuming monodisperse particles and a constant collision frequency function. They compared very well to the numerical prediction by a monodisperse model and reasonably well to that by MOMIC, suggesting the analytical solutions to be a simple first approximation in assessing the performance of CVD and flame synthesis methods of producing CNTs.     

MRI profiles over very wide concentration ranges: Application to swelling of a bentonite clay

In MRI investigation of soils, clays, and rocks, mainly mobile water is detected, similarly to that in biological and medical samples. However, the spin relaxation properties of water in these materials and/or low water concentration may make it difficult to use standard MRI approaches. Despite these limitations, one can combine MRI techniques developed for solid and liquid states and use independent information on relaxation properties of water, interacting with the material of interest, to obtain true images of both water and material content. We present procedures for obtaining such true density maps and demonstrate their use for studying the swelling of bentonite clay by water. A constant time imaging protocol provides 1D mapping of the clay distribution in regions with clay concentration above 10 vol%. T₁ relaxation time imaging is employed to monitor the clay content down to 10⁻³ vol%. Data provided by those two approaches are in good agreement in the overlapping range of concentrations. Covering five orders of magnitude of clay concentration, swelling of sodium-exchanged bentonite clays from pre-compacted pellets into a gel phase is followed in detail.     

13C direct detected COCO-TOCSY: a tool for sequence specific assignment and structure determination in protonless NMR experiments

A novel experiment is proposed to provide inter-residue sequential correlations among carbonyl spins in (13)C detected, protonless NMR experiments. The COCO-TOCSY experiment connects, in proteins, two carbonyls separated from each other by three, four or even five bonds. The quantitative analysis provides structural information on backbone dihedral angles phi as well as on the side chain dihedral angles of Asx and Glx residues. This is the first dihedral angle constraint that can be obtained via a protonless approach. About 75% of backbone carbonyls in Calbindin D(9K), a 75 amino acid dicalcium protein, could be sequentially connected via a COCO-TOCSY spectrum. 49 [Formula: see text] values were measured and related to backbone phi angles. Structural information can be extended to the side chain orientation of aminoacids containing carbonyl groups. Additionally, long range homonuclear coupling constants, (4)J(CC) and (5)J(CC), could be measured. This constitutes an unprecedented case for proteins of medium and small size.     

Fluctuation corrections at first order phase transitions: Application to C60

The temperature dependence of the elastic constants in C₆₀ is quite unusual in the vicinity of the order-disorder phase transition at 260 K, in sharp contrast to simple mean-field calculations. The observed deviations seem to be a combination of dynamical processes, the influence of defects and fluctuation effects. The latter are expected to be important, since the Landau free energy admits a third order term in the order parameter. We develop field theoretic perturbation theory for general models of this type. The formalism is applied to a simple scalar model of C₆₀ and the resulting temperature dependence of elastic constants is discussed.     

Experimental study of carbon materials behavior under high temperature and VUV radiation: Application to Solar Probe+ heat shield

The aim of the Solar Probe Plus (SP+) mission is to understand how the solar corona is heated and how the solar wind is accelerated. To achieve these goals, in situ measurements are necessary and the spacecraft has to approach the Sun as close as 9.5 solar radii. This trajectory induces extreme environmental conditions such as high temperatures and intense Vacuum Ultraviolet radiation (VUV). To protect the measurement and communication instruments, a heat shield constituted of a carbon material is placed on the top of the probe. In this study, the physical and chemical behavior of carbon materials is experimentally investigated under high temperatures (1600-2100 K), high vacuum (10⁻⁴ Pa) and VUV radiation in conditions near those at perihelion for SP+. Thanks to several in situ and ex situ characterizations, it was found that VUV radiation induced modification of outgassing and of mass loss rate together with alteration of microstructure and morphology.     

C3 or C4 macrophytes: a specific carbon source for the development of semi-aquatic and terrestrial arthropods in central Amazonian river-floodplains according to delta13C values

C4 plant species were proposed to generally represent inferior food sources compared to C3 plants thus are avoided by herbivores, particularly insects. This was tested in semi-aquatic and terrestrial arthropods from Amazonian river-floodplains by carbon isotope discrimination (delta13C). Two semi-aquatic grasshopper species (Stenacris f. fissicauda, Tucavaca gracilis-Acrididae) obtain their carbon during development from specific C4 macrophytes and two semi-aquatic species (Cornops aquaticum-Acrididae, Paulinia acuminata-Pauliniidae) from specific C3 macrophytes. The terrestrial millipede Mestosoma hylaeicum (Paradoxosomatidae) obtains about 45% of its carbon from roots of one C4 macrophyte during the development of immatures whereas adults use other food sources, including C3 trees. Results suggest, that (1) both C4 and C3 plants represent distinct hosts for terrestrial arthropods in Amazonia; (2) immatures may use plant species with a different photosynthetic pathway than adults.