T1 Relaxation Rates Research Articles

Longitudinal T1 relaxation rate (R1) captures changes in short-term Mn exposure in welders

Longitudinal T1 relaxation rate (R1) captures changes in short-term Mn exposure in welders

Effects of magnetization transfer on T1 contrast in human brain white matter

MRI based on T1 relaxation contrast is increasingly being used to study brain morphology and myelination. Although it provides for excellent distinction between the major tissue types of gray matter, white matter, and CSF, reproducible quantification of T1 relaxation rates is difficult due to the complexity of the contrast mechanism and dependence on experimental details. In this work, we perform simulations and inversion-recovery MRI measurements at 3T and 7T to show that substantial measurement variability results from unintended and uncontrolled perturbation of the magnetization of MRI-invisible 1H protons of lipids and macromolecules. This results in bi-exponential relaxation, with a fast component whose relative contribution under practical conditions can reach 20%. This phenomenon can strongly affect apparent relaxation rates, affect contrast between tissue types, and result in contrast variations over the brain. Based on this novel understanding, ways are proposed to minimize this experimental variability and its effect on T1 contrast, quantification accuracy and reproducibility.

Peculiarities of tissue water fractional composition in case of experimental whole-body hyperthermia

The present study, using proton nuclear magnetic resonance relaxation (NMR) method, was undertaken to compare the water fractional composition in nature tissues (group 1) with those damaged by experimental whole-body hyperthermia (group 2). We measured longitudinal or “spin-lattice” (T1) and transverse or “spin-spin” (T2) relaxation times of protons of tissues (brain, the atria of the heart, the kidneys and the renal cortex) from adult Wistar rats. The differences in T1, T2 and percentage of the intra- and extracellular water between group 1 and 2 were studied to help understand how the water moves in tissues at hyperthermia. The results of this study and the literature data allow to make conclusions about tissue water fractional composition in case of experimental whole-body hyperthermia: (1) fractional composition of water and the distribution of intra- and extracellular fluid in the tissue of the atria of the heart did not change (T1 and T2 relaxation times remained unchanged); (2) the crystalline water fraction increased in brain (longer T1 relaxation rate and shorter T2 relaxation rate). This is obstructing the exchange of protons between free and bound water in brain. Thus, loss of water by brain cells is prevented. The distribution between intra- and extracellular fluid in brain remained unchanged; (3) fraction of free water increased in renal tissue (simultaneous longer T1 and T2 relaxation rates) by reducing the volume of extracellular fluid; (4) thick hydration layer of water (longer T1 relaxation rate, T2 remained unchanged) was formed in the extracellular fluid of renal cortex. This water layer is formed around the sodium ions which concentration is increased in renal cortex tissue of rats from group 2. Аs a result, the amount of fluid secreted by kidneys is reduced, i.e. there is a retention of water in the body. The relevance of our research for the understanding of high temperatures’ adaptation mechanisms is discussed in this paper.

Mapping Radiation Injury and Recovery in Bone Marrow Using 18F-FLT PET/CT and USPIO MRI in a Rat Model.

We present and test the use of multimodality imaging as a topological tool to map the amount of the body exposed to ionizing radiation and the location of exposure, which are important indicators of survival and recovery. To achieve our goal, PET/CT imaging with 3'-deoxy-3'-(18)F-fluorothymidine ((18)F-FLT) was used to measure cellular proliferation in bone marrow (BM), whereas MRI using ultra-small superparamagnetic iron oxide (USPIO) particles provided noninvasive information on radiation-induced vascular damage. Animals were x-ray-irradiated at a dose of 7.5 Gy with 1 of 3 radiation schemes-whole-body irradiation, half-body shielding (HBS), or 1-leg shielding (1LS)-and imaged repeatedly. The spatial information from the CT scan was used to segment the region corresponding to BM from the PET scan using algorithms developed in-house, allowing for quantification of proliferating cells, and BM blood volume was estimated by measuring the changes in the T2 relaxation rates (ΔR2) collected from MR scans. (18)F-FLT PET/CT imaging differentiated irradiated from unirradiated BM regions. Two days after irradiation, proliferation of 1LS animals was significantly lower than sham (P = 0.0001, femurs; P < 0.0001, tibias) and returned to sham levels by day 10 (P = 0.6344, femurs; P = 0.3962, tibias). The degree of shielding affected proliferation recovery, showing an increase in the irradiated BM of the femurs, but not the tibias, of HBS animals when compared with 1LS (P = 0.0310, femurs; P = 0.5832, tibias). MRI of irradiated spines detected radiation-induced BM vascular damage, measured by the significant increase in ΔR2 2 d after whole-body irradiation (P = 0.0022) and HBS (P = 0.0003) with a decreasing trend of values, returning to levels close to baseline over 10 d. Our data were corroborated using γ-counting and histopathology. We demonstrated that (18)F-FLT PET/CT and USPIO MRI are valuable tools in mapping regional radiation exposure and the effects of radiation on BM. Analysis of the (18)F-FLT signal allowed for a clear demarcation of exposed BM regions and elucidated the kinetics of BM recovery, whereas USPIO MRI was used to assess vascular damage and recovery.

T1 Relaxation Rate (R1) Indicates Nonlinear Mn Accumulation in Brain Tissue of Welders With Low-Level Exposure.

Although the essential element manganese (Mn) is neurotoxic at high doses, the effects of lower exposure are unclear. MRI T1-weighted (TIW) imaging has been used to estimate brain Mn exposure via the pallidal index (PI), defined as the T1W intensity ratio in the globus pallidus (GP) versus frontal white matter (FWM). PI may not, however, be sensitive to Mn in GP because Mn also may accumulate in FWM. This study explored: (1) whether T1 relaxation rate (R1) could quantify brain Mn accumulation more sensitively; and (2) the dose-response relationship between estimated Mn exposure and T1 relaxation rate (R1). Thirty-five active welders and 30 controls were studied. Occupational questionnaires were used to estimate hours welding in the past 90 days (HrsW) and lifetime measures of Mn exposure. T1W imaging and T1-measurement were utilized to generate PI and R1 values in brain regions of interest (ROIs). PI did not show a significant association with any measure of Mn and/or welding-related exposure. Conversely, in several ROIs, R1 showed a nonlinear relationship to HrsW, with R1 signal increasing only after a critical exposure was reached. The GP had the greatest rate of Mn accumulation. Welders with higher exposure showed significantly higher R1 compared either with controls or with welders with lower exposure. Our data are additional evidence that Mn accumulation can be assessed more sensitively by R1 than by PI. Moreover, the nonlinear relationship between welding exposure and Mn brain accumulation should be considered in future studies and policies.

Simultaneous Imaging of CBF Change and BOLD with Saturation-Recovery-T1 Method

A neuroimaging technique based on the saturation-recovery (SR)-T1 MRI method was applied for simultaneously imaging blood oxygenation level dependence (BOLD) contrast and cerebral blood flow change (ΔCBF), which is determined by CBF-sensitive T1 relaxation rate change (ΔR1 CBF). This technique was validated by quantitatively examining the relationships among ΔR1 CBF, ΔCBF, BOLD and relative CBF change (rCBF), which was simultaneously measured by laser Doppler flowmetry under global ischemia and hypercapnia conditions, respectively, in the rat brain. It was found that during ischemia, BOLD decreased 23.1±2.8% in the cortical area; ΔR1 CBF decreased 0.020±0.004s-1 corresponding to a ΔCBF decrease of 1.07±0.24 ml/g/min and 89.5±1.8% CBF reduction (n=5), resulting in a baseline CBF value (=1.18 ml/g/min) consistent with the literature reports. The CBF change quantification based on temperature corrected ΔR1 CBF had a better accuracy than apparent R1 change (ΔR1 app); nevertheless, ΔR1 app without temperature correction still provides a good approximation for quantifying CBF change since perfusion dominates the evolution of the longitudinal relaxation rate (R1 app). In contrast to the excellent consistency between ΔCBF and rCBF measured during and after ischemia, the BOLD change during the post-ischemia period was temporally disassociated with ΔCBF, indicating distinct CBF and BOLD responses. Similar results were also observed for the hypercapnia study. The overall results demonstrate that the SR-T1 MRI method is effective for noninvasive and quantitative imaging of both ΔCBF and BOLD associated with physiological and/or pathological changes.

Correlation between relaxometry and diffusion tensor imaging in the globus pallidus of Huntington's disease patients.

Huntington's disease (HD) is an inherited neurodegenerative disorder with progressive impairment of motor, behavioral and cognitive functions. The clinical features of HD are closely related to the degeneration of the basal ganglia, predominantly the striatum. The main striatal output structure, the globus pallidus, strongly accumulates metalloprotein-bound iron, which was recently shown to influence the diffusion tensor scalar values. To test the hypothesis that this effect dominates in the iron-rich basal ganglia of HD patients, we examined the globus pallidus using DTI and T2 relaxometry sequences. Quantitative magnetic resonance (MR), clinical and genetic data (number of CAG repeats) were obtained from 14 HD patients. MR parameters such as the T2 relaxation rate (RR), fractional anisotropy (FA) and mean diffusivity (MD) were analysed. A positive correlation was found between RR and FA (R2=0.84), between CAG and RR (R2=0.59) and between CAG and FA (R2=0.44). A negative correlation was observed between RR and MD (R2=0.66). A trend towards correlation between CAG and MD was noted. No correlation between MR and clinical parameters was found. Our results indicate that especially magnetic resonance FA measurements in the globus pallidus of HD patients may be strongly affected by metalloprotein-bound iron accumulation.

T1 Relaxation Rate (R1) Indicates Nonlinear Mn Accumulation in Brain Tissue of Welders With Low-Level Exposure

T1 Relaxation Rate (R1) Indicates Nonlinear Mn Accumulation in Brain Tissue of Welders With Low-Level Exposure

Identification of lithium–sulfur battery discharge products through 6Li and 33S solid-state MAS and 7Li solution NMR spectroscopy

6Li and 33S solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy was used to identify the discharge products in lithium–sulfur (Li–S) battery cathodes. Cathodes were stopped at different potentials throughout battery discharge and measured ex-situ to obtain chemical shifts and T2 relaxation rates of the products formed. The chemical shifts in the spectra of both 6Li and 33S NMR demonstrate that long-chain, soluble lithium polysulfide species formed at the beginning of discharge are indistinguishable from each other (similar chemical shifts), while short-chain, insoluble polysulfide species that form at the end of discharge (presumably Li2S2 and Li2S) have a different chemical shift, thus distinguishing them from the soluble long-chain products. T2 relaxation measurements of discharged cathodes were also performed which resulted in two groupings of T2 rates that follow a trend and support the previous conclusions that long-chain polysulfide species are converted to shorter chain species during discharge. Through the complementary techniques of 1-D 6Li and 33S solid-state MAS NMR spectroscopy, solution 7Li and 1H NMR spectroscopy, and T2 relaxation rate measurements, structural information about the discharge products of Li–S batteries is obtained.

SU-E-T-105: Development of 3D Dose Verification System for Volumetric Modulated Arc Therapy Using Improved Polyacrylamide-Based Gel Dosimeter

Purpose: The aim of this dosimetric study was to develop 3D dose verification system for volumetric modulated arc therapy (VMAT) using polyacrylamide-based gel (PAGAT) dosimeter improved the sensitivity by magnesium chloride (MgCl2). Methods: PAGAT gel containing MgCl2 as a sensitizer was prepared in this study. Methacrylic-acid-based gel (MAGAT) was also prepared to compare the dosimetric characteristics with PAGAT gel. The cylindrical glass vials (4 cm diameter, 12 cm length) filled with each polymer gel were irradiated with 6 MV photon beam using Novalis Tx linear accelerator (Varian/BrainLAB). The irradiated polymer gel dosimeters were scanned with Signa 1.5 T MRI system (GE), and dose calibration curves were obtained using T2 relaxation rate (R2 = 1/T2). Dose rate (100-600 MU min−1) and fractionation (1-8 fractions) were varied. In addition, a cubic acrylic phantom (10 × 10 × 10 cm3) filled with improved PAGAT gel inserted into the IMRT phantom (IBA) was irradiated with VMAT (RapidArc). C-shape structure was used for the VMAT planning by the Varian Eclipse treatment planning system (TPS). The dose comparison of TPS and measurements with the polymer gel dosimeter was accomplished by the gamma index analysis, overlaying the dose profiles for a set of data on selected planes using in-house developed software. Results: Dose rate and fractionation dependence of improved PAGAT gel were smaller than MAGAT gel. A high similarity was found by overlaying the dose profiles measured with improved PAGAT gel dosimeter and the TPS dose, and the mean pass rate of the gamma index analysis using 3%/3 mm criteria was achieved 90% on orthogonal planes for VMAT using improved PAGAT gel dosimeter. Conclusion: In-house developed 3D dose verification system using improved polyacrylamide-based gel dosimeter had a potential as an effective tool for VMAT QA.

The feasibility of formation and kinetics of NMR signal amplification by reversible exchange (SABRE) at high magnetic field (9.4 T).

1H NMR signal amplification by reversible exchange (SABRE) was observed for pyridine and pyridine-d5 at 9.4 T, a field that is orders of magnitude higher than what is typically utilized to achieve the conventional low-field SABRE effect. In addition to emissive peaks for the hydrogen spins at the ortho positions of the pyridine substrate (both free and bound to the metal center), absorptive signals are observed from hyperpolarized orthohydrogen and Ir-complex dihydride. Real-time kinetics studies show that the polarization build-up rates for these three species are in close agreement with their respective 1H T1 relaxation rates at 9.4 T. The results suggest that the mechanism of the substrate polarization involves cross-relaxation with hyperpolarized species in a manner similar to the spin-polarization induced nuclear Overhauser effect. Experiments utilizing pyridine-d5 as the substrate exhibited larger enhancements as well as partial H/D exchange for the hydrogen atom in the ortho position of pyridine and concomitant formation of HD molecules. While the mechanism of polarization enhancement does not explicitly require chemical exchange of hydrogen atoms of parahydrogen and the substrate, the partial chemical modification of the substrate via hydrogen exchange means that SABRE under these conditions cannot rigorously be referred to as a non-hydrogenative parahydrogen induced polarization process.

The interplay of T1- and T2-relaxation on T1-weighted MRI of hMSCs induced by Gd-DOTA-peptides

Three Gd-DOTA-peptide complexes with different peptide sequence are synthesized and used as T1 contrast agent to label human mesenchymal stem cells (hMSCs) for magnetic resonance imaging study. The peptides include a universal cell penetrating peptide TAT, a linear MSC-specific peptide EM7, and a cyclic MSC-specific peptide CC9. A significant difference in labeling efficacy is observed between the Gd-DOTA-peptides as well as a control Dotarem. All Gd-DOTA-peptides as well as Dotarem induce significant increase in T1 relaxation rate which is in favor of T1-weighted MR imaging. Gd-DOTA-CC9 yields the maximum labeling efficacy but poor T1 contrast enhancement. Gd-DOTA-EM7 yields the minimum labeling efficacy but better T1 contrast enhancement. Gd-DOTA-TAT yields a similar labeling efficacy as Gd-DOTA-CC9 and similar T1 contrast enhancement as Gd-DOTA-EM7. The underlying mechanism that governs T1 contrast enhancement effect is discussed. Our results suggest that T1 contrast enhancement induced by Gd-DOTA-peptides depends not only on the introduced cellular Gd content, but more importantly on the effect that Gd-DOTA-peptides exert on the T1-relaxation and T2-relaxation processes/rates. Both T1 and particularly T2 relaxation rate have to be taken into account to interpret T1 contrast enhancement. In addition, the interpretation has to be based on cellular instead of aqueous longitudinal and transverse relaxivities of Gd-DOTA-peptides.

Water Proton Relaxivity, Superoxide Dismutase-like Activity, and Cytotoxicity of a Manganese(III) Porphyrin Having Four Poly(ethylene glycol) Tails

Abstract A high-molecular-weight water-soluble manganese(III) porphyrin having four poly(ethylene glycol) tails was prepared, which enhanced the T1 relaxation rate of water protons by ca. 7.5-fold compared with manganese(III)–tetra(4-sulfonatophenyl)porphyrin. The new compound also exhibited superoxide dismutase-like activity and significantly lower cytotoxicity.

In Situ 13C and 23Na Magic Angle Spinning NMR Investigation of Supercritical CO2 Incorporation in Smectite–Natural Organic Matter Composites

This Article presents an in situ NMR study of clay–natural organic polymer systems (a hectorite–humic acid [HA] composite) under CO2 storage reservoir conditions (90 bar CO2 pressure, 50 °C). The 13C and 23Na NMR data show that supercritical CO2 interacts more strongly with the composite than with the base clay and does not react to form other C-containing species over several days at elevated CO2. With and without organic matter, the data suggest that CO2 enters the interlayer space of Na–hectorite equilibrated at 43% relative humidity. The presence of supercritical CO2 also leads to increased 23Na signal intensity, reduced line width at half height, increased basal width, more rapid 23Na T1 relaxation rates, and a shift to more positive resonance frequencies. Larger changes are observed for the hectorite–HA composite than for the base clay. In light of recently reported MD simulations of other polymer–Na–smectite composites, we interpret the observed changes to be due to an increase in the rate of Na+ s...

Parallelizing acquisitions of solid-state NMR spectra with multi-channel probe and multi-receivers: Applications to nanoporous solids

A five-channel (1H, 19F, 31P, 27Al, 13C) 2.5mm magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) probe is used in combination with three separate receivers for the parallel acquisitions of one (1D) and two-dimensional (2D) NMR spectra in model fluorinated aluminophosphate and porous Al-based metal-organic framework (MOF). Possible combinations to record simultaneously spectra using this set-up are presented, including (i) parallel acquisitions of quantitative 1D NMR spectra of solids containing nuclei with contrasted T1 relaxation rates and (ii) parallel acquisitions of 2D heteronuclear NMR spectra. In solids containing numerous different NMR-accessible nuclei, the number of NMR experiments that have to be acquired to get accurate structural information is high. The strategy we present here, i.e. the multiplication of both the number of irradiation channels in the probe and the number of parallel receivers, offers one possibility to optimize this measurement time.

MRI‐Visualized, Dual‐Targeting, Combined Tumor Therapy Using Magnetic Graphene‐Based Mesoporous Silica

Targeting peptide-modified magnetic graphene-based mesoporous silica (MGMSPI) are synthesized, characterized, and developed as a multifunctional theranostic platform. This system exhibits many merits, such as biocompatibility, high near-infrared photothermal heating, facile magnetic separation, large T2 relaxation rates (r2), and a high doxorubicin (DOX) loading capacity. In vitro and in vivo results demonstrate that DOX-loaded MGMSPI (MGMSPID) can integrate magnetic resonance imaging, dual-targeting recognition (magnetic targeting and receptor-mediated active targeting), and chemo-photothermal therapy into a single system for a visualized-synergistic therapy of glioma. In addition, it is observed that the MGMSPID system has heat-stimulated, pH-responsive, sustained release properties. All of these characteristics would provide a robust multifunctional theranostic platform for visualized glioma therapy.

Implementation of P22 Viral Capsids As Intravascular Magnetic Resonance T1 Contrast Conjugates via Site-Selective Attachment of Gd(III)-Chelating Agents

P22 viral capsids and ferritin protein cages are utilized as templating macromolecules to conjugate Gd(III)-chelating agent complexes, and we systematically investigates the effects of the macromolecules' size and the conjugation positions of Gd(III)-chelating agents on the magnetic resonance (MR) relaxivities and the resulting image contrasts. The relaxivity values of the Gd(III)-chelating agent-conjugated P22 viral capsids (outer diameter: 64 nm) are dramatically increased as compared to both free Gd(III)-chelating agents and Gd(III)-chelating agent-conjugated ferritins (outer diameter: 12 nm), suggesting that the large sized P22 viral capsids exhibit a much slower tumbling rate, which results in a faster T1 relaxation rate. Gd(III)-chelating agents are attached to either the interior or exterior surface of P22 viral capsids and the conjugation positions of Gd(III)-chelating agents, however, do not have a significant effect on the relaxivity values of the macromolecular conjugates. The contrast enhancement of Gd(III)-chelating agent-conjugated P22 viral capsids is confirmed by in vitro phantom imaging at a short repetition times (TR) and the potential usage of Gd(III)-chelating agent-conjugated P22 viral capsids for in vivo MR imaging is validated by visualizing a mouse's intravascular system, including the carotid, mammary arteries, the jugular vein, and the superficial vessels of the head at an isotropic resolution of 250 μm.

Skeletal muscle evaluation by MRI in a rabbit model of acute ischaemia

To assess rhabdomyolysis-associated skeletal muscle changes induced by complete ischaemia in rabbits using MRI. Acute ischaemia was induced in the right hind limb of 34 New Zealand white rabbits by arterial ligation. MRI of vastus lateralis was carried out pre-operatively and every hour post-operatively up to 7 h. T1 weighted images, T2 weighted images with fat suppression, T2 maps and diffusion tensor scans were obtained. The correlation of MRI findings with histopathological changes in biopsies of vastus lateralis was examined. Histopathology demonstrated early cellular oedema 1 h post ischaemia and irreversible injuries by 7 h, including loss of striation and broken muscle fibres. T2 weighted images with fat suppression showed inhomogeneous high signal intensity of vastus lateralis, which progressively increased from 2 h following ischaemia. The T2 relaxation rate of ischaemic vastus lateralis was significantly greater than normal muscle (p<0.001) and demonstrated a linear increase with time following ischaemia. A similar linear increase was also found in the ischaemic vastus lateralis apparent diffusion coefficient (ADC) 1-5 h post ischaemia (p=0.006). Both the T2 ADC and fractional anisotropy (FA) were significantly higher on the ischaemic side 7 h post ischaemia (for T2, p=0.02; for ADC, p=0.004). Muscle oedema is detectable on MR images and is reflected well by T2, ADC and FA values. MRI may have value in clinical evaluation of rhabdomyolysis. Ischaemic changes detected by MRI may have value in the diagnosis of rhabdomyolysis.

Bifunctional heterometallic Ln3+–Gd3+(Ln = Eu, Tb) hybrid silica microspheres: luminescence and MRI contrast agent property

A novel series of homometallic and heterometallic lanthanide (Eu(3+)(Tb(3+))-Gd(3+)) hybrid silica microspheres (EDTA-(Eu(Tb)-Gd)-TTA-SiO(2)) are synthesized with 2-thenoyltrifluoroacetone (TTA) functionalized silane and ethylenediaminetetraacetic acid (EDTA) by sol-gel process, whose physical characterization are carried out and especially the luminescence and the magnetic resonance imaging (MRI) contrast agent properties are discussed. These hybrids present uniform silica microsphere morphology with particle size of 1 μm. Comparing to the homometallic hybrid silica microsphere EDTA-Ln-TTA-SiO(2) without Gd(3+) ion, the heterometallic hybrid silica microspheres EDTA-Eu-Gd-TTA-SiO(2) exhibit stronger luminescent intensity, longer lifetime and higher luminescent quantum efficiency, which is due to the fact that inert ion Gd(3+) can enhance the luminescence of the Eu(3+) or Tb(3+) within the hybrid system. In addition, the MRI relaxivity of the heterometallic lanthanide hybrid silica microspheres in water is assessed, showing a lower T1 relaxation rate than homometallic gadolinium hybrid one (EDTA-Gd-TTA-SiO(2)). Both of them show higher T1 relaxation rate than the conventional Gd chelate of diethylenetriamine pentaacetic acid. These bifunctional hybrid materials exhibit both luminescent and MRI magnetic contrast agent properties, whose further investigation can be expected to have potential application in practical fields such as optical storage and sensors, etc.

Study of an S = 1 NiII pincer electrocatalyst precursor for aqueous hydrogen production based on paramagnetic 1H NMR

A tridentate NNN Ni(II) complex, shown to be an electrocatalyst for aqueous H2 production at low overpotentials, is studied by using temperature-dependent paramagnetic (1)H NMR. The NMR T1 relaxation rates, temperature dependence of the chemical shifts, and dc SQUID magnetic susceptibility are correlated to DFT chemical shifts and compared with the properties of a diamagnetic Zn analogue complex. The resulting characterization provides an unambiguous assignment of the six proton environments in the meridionally coordinating tridentate NNN ligand. The demonstrated NMR/DFT methodology should be valuable in the search for appropriate ligands to optimize the reactivity of 3d metal complexes bound to attract increasing attention in catalytic applications.