3D to 0D cesium lead bromide: A 79/81Br NMR, NQR and theoretical investigation.

Inorganic metal halides offer unprecedented tunability through elemental variation of simple three-element compositions, but can exhibit complicated phase behaviour, degradation, and microscopic phenomena (disorder/dynamics) that play an integral role for the bulk-level chemical and physical properties of these materials. Understanding the halogen chemical environment in such materials is crucial to addressing many of the concerns regarding implementing these materials in commercial applications. In this study, a combined solid-state nuclear magnetic resonance, nuclear quadrupole resonance and quantum chemical computation approach is used to interrogate the Br chemical environment in a series of related inorganic lead bromide materials: CsPbBr3, CsPb2Br5, and Cs4PbBr6. The quadrupole coupling constants (CQ) were determined to range from 61 to 114 MHz for 81Br, with CsPbBr3 exhibiting the largest measured CQ and Cs4PbBr6 the smallest. GIPAW DFT was shown to be an excellent pre-screening tool for estimating the EFG of Br materials and can increase experimental efficiency by providing good starting estimates for acquisition. Finally, the combination of theory and experiment to inform the best methods for expanding further to the other quadrupolar halogens is discussed.

Theory of chemical exchange saturation transfer MRI in the context of different magnetic fields.

Chemical exchange saturation transfer (CEST) magnetic resonance imaging (MRI) is a versatile MRI method that provides contrast based on the level of molecular and metabolic activity. This contrast arises from indirect measurement of protons in low concentration molecules that are exchanging with the abundant water proton pool. The indirect measurement is based on magnetization transfer of radio frequency (rf)-prepared magnetization from the small pool to the water pool. The signal can be modeled by the Bloch-McConnell equations combining standard magnetization dynamics and chemical exchange processes. In this article, we review analytical solutions of the Bloch-McConnell equations and especially the derived CEST signal equations and their implications. The analytical solutions give direct insight into the dependency of measurable CEST effects on underlying parameters such as the exchange rate and concentration of the solute pools, but also on the system parameters such as the rf irradiation field B1 , as well as the static magnetic field B0 . These theoretical field-strength dependencies and their influence on sequence design are highlighted herein. In vivo results of different groups making use of these field-strength benefits/dependencies are reviewed and discussed.

Metabolic and transcriptomic profiles of glioblastoma invasion revealed by comparisons between patients and corresponding orthotopic xenografts in mice.

The invasive behavior of glioblastoma, the most aggressive primary brain tumor, is considered highly relevant for tumor recurrence. However, the invasion zone is difficult to visualize by Magnetic Resonance Imaging (MRI) and is protected by the blood brain barrier, posing a particular challenge for treatment. We report biological features of invasive growth accompanying tumor progression and invasion based on associated metabolic and transcriptomic changes observed in patient derived orthotopic xenografts (PDOX) in the mouse and the corresponding patients' tumors. The evolution of metabolic changes, followed in vivo longitudinally by 1H Magnetic Resonance Spectroscopy (1H MRS) at ultra-high field, reflected growth and the invasive properties of the human glioblastoma transplanted into the brains of mice (PDOX). Comparison of MRS derived metabolite signatures, reflecting temporal changes of tumor development and invasion in PDOX, revealed high similarity to spatial metabolite signatures of combined multi-voxel MRS analyses sampled across different areas of the patients' tumors. Pathway analyses of the transcriptome associated with the metabolite profiles of the PDOX, identified molecular signatures of invasion, comprising extracellular matrix degradation and reorganization, growth factor binding, and vascular remodeling. Specific analysis of expression signatures from the invaded mouse brain, revealed extent of invasion dependent induction of immune response, recapitulating respective signatures observed in glioblastoma. Integrating metabolic profiles and gene expression of highly invasive PDOX provided insights into progression and invasion associated mechanisms of extracellular matrix remodeling that is essential for cell-cell communication and regulation of cellular processes. Structural changes and biochemical properties of the extracellular matrix are of importance for the biological behavior of tumors and may be druggable. Ultra-high field MRS reveals to be suitable for in vivo monitoring of progression in the non-enhancing infiltration zone of glioblastoma.

Survey of mosses (Bryophyta) along visitor trails in the Parque Nacional do Caparaó, Espírito Santo State, Brazil / Levantamento de musgos (Bryophyta) em trilhas de visitação no Parque Nacional do Caparaó, Estado do Espírito Santo, Brasil

Bryophyta, the mosses, are an abundant plant group in humid environments. In the Atlantic Coastal Forest of Southeastern Brazil, they are found in great richness and diversity, especially in the montane regions.  In this context, the Parque Nacional do Caparaó, where our study was conducted, is known for its mountain environment and high altitude. Although a considerable number of moss collections from the western part of the park is already deposited in herbaria, the eastern side belonging to the state of Espírito Santo State had been undersampled until now. For this pioneering work, we covered the park's main visitation trails during three intensive days of collections. We found 59 species of mosses, belonging to 38 genera and 22 families. Nine species are new occurrences for the state and 14 are Brazilian endemics. Most species were found growing on soil. We found more species at altitudes above 1,500 m a.s.l. Sematophyllaceae was the richest moss family.

No Brasil, os musgos (Bryophyta) são encontrados com maior riqueza e diversidade na Mata Atlântica, especialmente em ambientes montanhosos e úmidos como o encontrado no Parque Nacional do Caparaó.  A coleta do material foi realizada durante três dias onde percorremos as principais trilhas de visitação do parque. Foram identificadas 59 espécies pertencentes a 38 gêneros e 22 famílias. Nove espécies são novas ocorrências para o Estado e 14 são endêmicas do país. A família mais rica em espécies foi Sematophyllaceae. As espécies terrícolas são as mais frequentes. A maior riqueza de espécies foi observada em altitudes acima de 1.500 m alt. Embora se tenha considerável número de coletas depositadas nos herbários, oriundos da porção oeste do parque, este é um trabalho pioneiro na região que se estende pelo Espírito Santo.

Achieving 1 ppm field homogeneity above 24 T: Application of differential mapping for shimming Keck and the Series Connected Hybrid magnets at the NHMFL.

Powered resistive and resistive-superconductive hybrid magnets can reach fields higher than superconducting NMR magnets but lack the field homogeneity and temporal stability needed for high resolution NMR. Due to field fluctuations in powered magnets, commercially available mapping systems fail to produce maps of these magnets with sufficient reproducibility, thus hampering attempts to improve homogeneity of the field they generate. Starting with a commercial mapper, we built a mapping system which uses a two-channel (measurement + reference) mapper probe. We used this system to map and then to shim two magnets of Florida Bitter type at the National High Magnetic Field Laboratory in Tallahassee, FL. With a combination of passive (ferromagnetic) and active shims we achieved 2.3 ppm homogeneity in 1 cm diameter spherical volume (dsv) at 25.0 T in the Keck resistive magnet, and 0.9 ppm homogeneity in 1 cm dsv at 23.5, 28.2, and 35.2 T in the series-connected resistive-superconductive hybrid (SCH) magnet.

Fast and efficient free induction decay MR spectroscopic imaging of the human brain at 9.4 Tesla.

PURPOSE: The purpose of this work was to develop a fast and efficient MRSI-FID acquisition scheme and test its performance in vivo. The aim was to find a trade-off between the minimal total acquisition time and signal-to-noise ratio of the acquired spectra. METHODS: Measurements were performed on a 9.4 Tesla system. Sequence optimization included redesign of water suppression, optimization of the sequence gradients, and improvement of the sampling efficiency by minimizing the read-out time. This resulted in an acquisition time of 2:47 and 22:13 minutes for 2D (TR = 57 ms; 3-mm in-plane resolution) and 3D MRSI (TR = 57 ms; 16 slices; 3-mm isotropic resolution), respectively. RESULTS: Despite strong T1 weighting and first-order phase problems, it was possible to obtain spectra of an acceptable quality. The average line width calculated for the tCr peak across the entire field of view was 26.9 ± 9.6 Hz for 2D and 30.0 ± 11.3 Hz for 3D MRSI. In 3D measurements, the percent fraction of voxels fitted with Cramer-Rao lower bounds below 10% was 53.3 ± 4.1%, 63.4 ± 8.4%, and 81.0 ± 2.9% for Glu, tCr, and tNAA, respectively. CONCLUSION: Considering the typically long duration of high-resolution MRSI, the proposed technique may be of interest for clinical applications and/or studies that focus on following the biochemistry of dynamic processes. Magn Reson Med 78:1281-1295, 2017. © 2016 International Society for Magnetic Resonance in Medicine.

Brain high-energy phosphates and creatine kinase synthesis rate under graded isoflurane anesthesia: An in vivo (31) P magnetization transfer study at 11.7 tesla.

PURPOSE: The creatine kinase rate of metabolic adenosine triphosphate (ATP) synthesis is an important metabolic parameter but is challenging to measure in vivo due to limited signal-to-noise ratio and long measurement time. THEORY AND METHODS: This study reports the implementation of an accelerated (31) P Four Angle Saturation Transfer (FAST) method to measure the forward creatine kinase (CK) rate of ATP synthesis. Along with a high-field scanner (11.7 Tesla) and a small sensitive surface coil, the forward CK rate in the rat brain was measured in ∼5 min. RESULTS: Under 1.2% isoflurane, the forward CK rate constant and metabolic flux were, respectively, kf , CK =0.26 ± 0.02 s(-1) and Ff,CK =70.8 ± 4.6 µmol/g/min. As a demonstration of utility and sensitivity, measurements were made under graded isoflurane. Under 2.0% isoflurane, kf , CK =0.16 ± 0.02 s(-1) and Ff,CK =410.0 ± 4.2 µmol/g/min, corresponding to a 38% and 42% reduction, respectively, relative to 1.2% isoflurane. By contrast, the ATP and phosphocreatine concentrations were unaltered. CONCLUSION: This study demonstrated the (31) P FAST measurement of creatine kinase rate of ATP synthesis in rat brain with reasonable temporal resolution. Different isoflurane levels commonly used in animal models significantly alter the CK reaction rate but not ATP and phosphocreatine concentrations.

Water-selective excitation of short T2 species with binomial pulses.

PURPOSE: For imaging of fibrous musculoskeletal components, ultra-short echo time methods are often combined with fat suppression. Due to the increased chemical shift, spectral excitation of water might become a favorable option at ultra-high fields. Thus, this study aims to compare and explore short binomial excitation schemes for spectrally selective imaging of fibrous tissue components with short transverse relaxation time (T2 ). METHODS: Water selective 1-1-binomial excitation is compared with nonselective imaging using a sub-millisecond spoiled gradient echo technique for in vivo imaging of fibrous tissue at 3T and 7T. RESULTS: Simulations indicate a maximum signal loss from binomial excitation of approximately 30% in the limit of very short T2 (0.1 ms), as compared to nonselective imaging; decreasing rapidly with increasing field strength and increasing T2 , e.g., to 19% at 3T and 10% at 7T for T2 of 1 ms. In agreement with simulations, a binomial phase close to 90° yielded minimum signal loss: approximately 6% at 3T and close to 0% at 7T for menisci, and for ligaments 9% and 13%, respectively. CONCLUSION: Overall, for imaging of short-lived T2 components, short 1-1 binomial excitation schemes prove to offer marginal signal loss especially at ultra-high fields with overall improved scanning efficiency.

NMR in pulsed high-field magnets and application to high-T(C) superconductors.

This article deals with the implementation of Nuclear Magnetic Resonance (NMR) experiments in pulsed magnetic fields at the pulsed-field facility of the Laboratoire National des Champs Magnétiques Intenses and its application to the high-T(C) superconductor YBa2Cu3O6.51. The experimental setup is described in detail, including a low-temperature probe head adapted for pulsed fields. An entire paragraph is dedicated to the discussion of NMR in pulsed field and the introduction of an advanced deconvolution technique making use of the induction voltage in an additional pick-up coil. The (63)Cu/(65)Cu NMR experiments on an YBa2Cu3O6.51 single crystal were performed at 2.5K during a field pulse of 46.8-T-amplitude. In the recorded spectrum the (63)Cu center line and high-frequency satellites as well as the (65)Cu center line are identified and are compared with results in literature.

Improved RF performance of travelling wave MR with a high permittivity dielectric lining of the bore.

Application of travelling wave MR to human body imaging is restricted by the limited peak power of the available RF amplifiers. Nevertheless, travelling wave MR advantages like a large field of view excitation and distant location of transmit elements would be desirable for whole body MRI. In this work, improvement of the B1+ efficiency of travelling wave MR is demonstrated. High permittivity dielectric lining placed next to the scanner bore wall effectively reduces attenuation of the travelling wave in the longitudinal direction and at the same time directs the radial power flow toward the load. First, this is shown with an analytical model of a metallic cylindrical waveguide with the dielectric lining next to the wall and loaded with a cylindrical phantom. Simulations and experiments also reveal an increase of B1+ efficiency in the center of the bore for travelling wave MR with a dielectric lining. Phantom experiments show up to a 2-fold gain in B1+ with the dielectric lining. This corresponds to a 4-fold increase in power efficiency of travelling wave MR. In vivo experiments demonstrate an 8-fold signal-to-noise ratio gain with the dielectric lining. Overall, it is shown that dielectric lining is a constructive method to improve efficacy of travelling wave MR.

High-resolution Fourier-encoded sub-millisecond echo time musculoskeletal imaging at 3 Tesla and 7 Tesla.

PURPOSE: The feasibility of imaging musculoskeletal fibrous tissue components, such as menisci, ligaments, and tendons, with a conventional spoiled gradient echo technique is explored in vivo at 3 T and 7 T. METHODS: To this end, the echo time (TE1 ) of a conventional Fourier-encoded multicontrast three-dimensional SGPR sequence is minimized by using nonselective excitation pulses, highly asymmetric readouts, and a variable TE1 along the phase and slice encoding direction. In addition, a fully sampled second echo image (with TE2 >> TE1 ) can be used to highlight components with short transverse relaxation times in a difference image with positive contrast. RESULTS: Fourier-encoded spoiled gradient echo sequences are able to provide sub-millisecond TE1 of about 800 µs for typical in-plane resolutions of about 0.5 x 0.5 mm(2) . As a result, high-resolution positive contrast images of fibrous tissues can be generated within clinically feasible scan-time of about 2-7 minutes. CONCLUSION: After optimization, Fourier-encoded spoiled gradient echo provides a highly robust and flexible imaging technique for high-resolution positive contrast imaging of fibrous tissue that can readily be used in the clinical routine.