Detection of T2 changes in an early mouse brain tumor

The aim of the study was to determine the effect of early tumor growth on T₂ relaxation times in an experimental glioma model. A 9.4-T magnetic resonance imaging (MRI) system was used for the investigations. An animal model (n=12) of glioma was established using an intracranial inoculation of U87MGdEGFRvIII cells. The imaging studies were performed from Day 10 through Day 13 following tumor inoculation. Tumor blood vessel density was determined using quantitative immunochemistry. Tumor volume was measured daily using MR images. T₂ values of the tumor were measured in five areas across the tumor and calculated using a single exponential fitting of the echo train. The measurements on Days 10 and 13 after tumor inoculation showed a 20% increase in T₂. The changes in T₂ correlated with the size of the tumor. Statistically significant differences in T₂ values were observed between the edge of the tumor and the brain tissue on Days 11, 12 and 13 (P=.014, .008, .001, respectively), but not on Day 10 (P=.364). The results show that T₂-weighted MRI may not detect glioma during an early phase of growth. T₂ increases in growing glioma and varies heterogenously across the tumor.     

3D spin-lock imaging of human gliomas

We investigated whether the simultaneous use of paramagnetic contrast medium and 3D on-resonance spin lock (SL) imaging could improve the contrast of enhancing brain tumors at 0.1 T. A phantom containing serial concentrations of gadopentetate dimeglumine (Gd-DTPA) in cross-linked bovine serum albumin (BSA) was imaged. Eleven patients with histologically verified glioma were also studied. T₁-weighted 3D gradient echo images with and without SL pulse were acquired before and after a Gd-DTPA injection. SL effect, contrast, and contrast-to-noise ratio (CNR) were calculated for each patient. In the glioma patients, the SL effect was significantly smaller in the tumor than in the white and gray matter both before (p = 0.001, p = 0.025, respectively), and after contrast medium injection (p < 0.001, p < 0.001, respectively). On post-contrast images, SL imaging significantly improved tumor contrast (p = 0.001) whereas tumor CNR decreased slightly (p = 0.024). The combined use of SL imaging and paramagnetic Gd-DTPA contrast agent offers a modality for improving tumor contrast in magnetic resonance imaging (MRI) of enhancing brain tumors. 3D gradient echo SL imaging has also shown potential to increase tissue characterization properties of MR imaging of human gliomas.     

Critical nuclear relaxation in cobalt metal

Nuclear magnetic resonance of cobalt metal was investigated in the paramagnetic and ferromagnetic states and in the critical region below T_c. The Knight shift and spin lattice relaxation times were measured in the paramagnetic phase in the solid and liquid states from 1578 K to 1825 K. The resonant frequency, spin-lattice and spin-spin relaxation times were measured in the ferromagnetic phase from room temperature to 1385 K. The main part of (T₁T)^-1 results from fluctuating orbital moments in both phases except near T_c where this process forms the background for critical spin relaxation. The critical exponents for T^-1₁ and for the magnetization in the ferromagnetic state were found to be n' = 0.96 ± 0.07 and β = 0.308 ± 0.012, respectively.     

Magnetic,optical and relaxometric properties of organically coated gold–magnetite (Au–Fe3O4) hybrid nanoparticles for potential use in biomedical applications

We present the magnetic, optical and relaxometric properties of multifunctional Au–Fe₃O₄ hybrid nanoparticles (HNPs), as possible novel contrast agents (CAs) for magnetic resonance imaging (MRI). The HNPs have been synthesized by wet chemical methods in heterodimer and core–shell geometries and capped with oleylamine. Structural characterization of the samples have been made by X-ray diffraction and transmission electron microscopy, while magnetic properties have been investigated by means of Superconducting Quantum Interference Device-SQUID magnetometry experiments. As required for MRI applications using negative CAs, the samples resulted superparamagnetic at room temperature and well above their blocking temperatures. Optical properties have been investigated by analyzing the optical absorbtion spectra collected in UV–visible region. Relaxometric measurements have been performed on organic suspensions of HNPs and Nuclear Magnetic Resonance (NMR) dispersion curves have been obtained by measuring the longitudinal 1/T₁ and transverse 1/T₂ relaxation rates of solvent protons in the range 10 kHz/300 MHz at room temperature. NMR relaxivities r₁ and r₂ have been compared with ENDOREM^®, one of the commercial superparamagnetic iron oxide based MRI contrast agents. MRI contrast enhancement efficiencies have been investigated also by examining T₂-weighted MR images of suspensions. The experimental results suggest that the nanoparticles' suspensions are good candidates as negative CAs.     

Radiotherapy effects on vertebral bone marrow: Easily recognizable changes in T2 relaxation times

The effect of localized radiotherapy on vertebral bone marrow was demonstrated in two patients using quantitative MRI studies with pixel-by-pixel measurement of T₂ relaxation times with generation of T₂ images. Conventional T₁-weighted spin-echo images were obtained as well. Irradiated vertebral bone marrow was found to have longer T₂ relaxation times than the neighboring nonirradiated bone marrow. These changes corresponded to the increased signal intensity on T₁-weighted images and to the field of radiotherapy and were noted 2.5 to 32 mo after radiotherapy. Radiologists should be aware of the increased T₂ relaxation times in irradiated bone marrow to correctly assess spinal disorders in irradiated patients. The reported T₂ changes may reflect the abundance of adipose cells that proliferate in bone marrow after radiotherapy, or may indicate an additional histological change, such as bone marrow necrosis or edema. Conclusive histological proof remains to be obtained.     

Anomalous magnetism and 209Bi nuclear spin relaxation in Bi4Ge3O12 crystals

The quadrupole ²⁰⁹Bi spin–spin and spin–lattice relaxation were studied within 4.2–300 K for pure and doped Bi₄Ge₃O₁₂ single crystals which exhibit, as was previously found, anomalous magnetic properties. The results revealed an unexpectedly strong influence of minor amounts of paramagnetic dopants (0.015–0.5 mol.%) on the relaxation processes. Various mechanisms (quadrupole, crystal electric field, electron spin fluctuations) govern the spin–lattice relaxation time T ₁ in pure and doped samples. Unlike T ₁, the spin–spin relaxation time T ₂ for pure and Nd-doped samples was weakly dependent on temperature within 4.2–300 K. Doping Bi₄Ge₃O₁₂ with paramagnetic atoms strongly elongated T ₂. The elongation, although not so strong, was also observed for pure and doped crystals under the influence of weak (～30 Oe) external magnetic fields. To confirm the conclusion about strong influence of crystal field effects on the temperature dependence of T ₁ in the temperature range 4.2–77 K, the magnetization vs. temperature and magnetic field was measured for Nd- and Gd-doped Bi₄Ge₃O₁₂ crystals using a SQUID magnetometer. The temperature behavior of magnetic susceptibility for the Nd-doped crystal was consistent with the presence of the crystal electric field effects. For the Gd-doped crystal, the Brillouin formula perfectly fitted the curve of magnetization vs. magnetic field, which pointed to the absence of the crystal electric field contribution into the spin–lattice relaxation process in this sample.     

A numerical prediction of spin-lattice relaxation enhancement of water protons by paramagnetic metal ions and free radicals. A contribution to the basic principles of relaxometry in MRI

The Solomon-Bloembergen and several simplified equations from literature are critically evaluated with the purpose of selecting an equation for rapid numerical predictions of spin-lattice relaxation data of water protons induced by paramagnetic transition metal and lanthanide ions and organic free radicals. The following equation is proposed for practical applications: $$\frac{1}{{T_1 }} \approx F\frac{{\pi ^2 \gamma _{\rm I} ^2 \gamma _S ^2 \hbar ^2 N}}{k} \frac{{m\eta }}{T} S(S + 1) \approx F 1.06^7 \frac{{m\eta }}{T} S(S + 1),$$ , whereT ₁ is the spin-lattice relaxation time, 1/T ₁ is the spin-lattice relaxation rate, γ₁ is the gyromagnetic ratio of the proton of water, γ_S is the gyromagnetic ratio of the electron,k is the Boltzman constant,h is the Plank constant, ? =h/2π,N is the number of paramagnetic species per cubic centimeter, i.e. the Avogadro number/1000,m is the concentration of the paramagnetic species in mM, η is the viscosity in centipoise at appropriate temperature,T is the appropriate absolute temperature,S is the spin quantum number, andF is a methodical factor which can range between 1–2.7, depending on the magnetic properties of the instrumentation, i.e. ～1.07 MHz (0.025 T)–90 MHz (2.1 T), and the relaxation enhancing agent. It is proposed to useF=1 for rapid numerical predictions. This equation is based on models involving translational motions and is suitable for rapid estimatesin vitro of spin-lattice relaxation times and rates of protons in water, and water protons in plasma and other biological fluids in the presence of paramagnetic metal ions, their low molecular weight complexes, and free radicals, as exemplified by nitroxyl (aminoxyl) radicals. Although this equation will be used for measurementsin vitro, the results could also be applied to project the effectiveness of new contrast agentsin vivo. It is believed that this equation will be useful in research involving the development of new contrast agents for MRI.     

Cerebral ischemic injury model of rat demonstrated withT 2-weighted magnetic resonance imaging

A photochemical reaction model of focal cerebral ischemic injury of rat was demonstrated by means of enhancedT ₂-weighted magnetic resonance imaging. The cerebral ischemia model was made using vein injection of rose bengal and irradiation by a beam of a cw laser with the wave-length of 514 nm. The ischemic injury region in rat brain can be found clearly in theT ₂-weighted magnetic resonance images in one hour, this time was calculated from the beginning of the laser irradiation to the end of the NMR data acquisition. It suggests thatT ₂-weighted imaging can find cerebral ischemia earlier than several hours after the onset of ischemia given in other papers. It also confirms that theT ₂-weighted magnetic resonance imaging approach should be of great potential to be applied in studying the cerebral ischemia.     

In vivo NMR imaging and T1 measurements of water protons in the human brain

Nuclear magnetic resonance (NMR) proton density images of the human brain have been made by the FONAR method. Spin-lattice relaxation times, T₁, of water hydrogen protons have been determined at random positions within frontal and temporal regions of the human brain. The primary purpose of this ongoing research is to accumulate a large data base of normal T₁ values for water protons in normal human brain tissue. Our experience to data includes 31 measurements on 18 volunteer subjects, and the mean value ± standard deviation is 215 ± 42 msec. In addition, two metastatic lesions of the brain were studied and found to have T₁ values longer than those for normal brain tissue.     

Particle size dependence of relaxivity for silica-coated iron oxide nanoparticles

We investigate the particle size dependence of the relaxivity of hydrogen protons in an aqueous solution of iron oxide (Fe₃O₄) nanoparticles coated in silica for biocompatibility. The T₁ and T₂ relaxation times for various concentrations of silica-coated nanoparticles were determined by a magnetic resonance scanner. We find that the relaxivity increased linearly with increasing particle size. The T₂ relaxivity (R₂) is more than 50 times larger than the T₁ relaxivity (R₁) for the nanoparticle contrast agent, which reflects the fact that the T₂ relaxation is mainly influenced by outer sphere processes. The high R₂/R₁ ratio demonstrates that silica-coated iron oxide nanoparticles may serve as a T₂ contrast agents in magnetic resonance imaging with high efficacy.     

Spin conversion detected by Mössbauer spectroscopy and μSR on a 1D FeII paramagnetic chain

While magnetic properties of the 1D chain [Fe(hyetrz)₃](4-bromophenylsulfonate)₂ investigated over the temperature range from 300 K to 2 K show paramagnetic behavior, detailed ⁵⁷Fe Mössbauer and muon spin relaxation measurements reveal an unexpected spin conversion. Approximately ~14 % of the high-spin ions are found to convert to the low-spin state with a transition temperature T _1/2?~?120 K.     

NMR studies of magnetic properties in Heusler-type Mn 3 Si

In order to microscopically investigate the magnetic properties of both paramagnetic and antiferromagnetic phases in Mn₃Si (T _N?=?23 K), the ⁵⁵Mn NMR has been carried out at temperatures between 2.2 K and 300 K. The temperature dependences of the spectrum, Knight shift (or resonance frequency shift) and spin-lattice relaxation time T ₁ of ⁵⁵Mn NMR have been measured. In the paramagnetic phase, only one resonance spectrum can be obtained. The observed spectrum is identified to be a signal corresponding to the Mn(II) site. In the antiferromagnetic phase, two different spectra corresponding to the Mn(I) and Mn(II) sites are found at the resonance frequencies of 145 and 6 MHz, respectively, by the zero field NMR at 4.2 K. From these results, the internal magnetic fields on the ⁵⁵Mn(I) and ⁵⁵Mn(II) nuclei are found to be 13.6 and 0.6 T, respectively. According to the NMR results, the helical structure in incommensurate Mn spin states is better explained compared with the transverse sinusoidal structure.     

Optorelaxers: Achieving real-time control of NMR relaxation

We present an approach to increase the detection sensitivity of NMR by shortening the spin-lattice relaxation time using transient paramagnetic species created by light irradiation of “optorelaxer” molecules. In the ultimate implementation of this concept, not yet realized here, these transient species are absent during the detection period, thereby avoiding the loss of spectral resolution caused by inhomogeneous broadening from paramagnetic species. Real-time control of NMR relaxation by visible light is demonstrated with Fe(II)(ptz)₆(BF₄)₂, (ptz = 1-propyltetrazole), abbreviated FePTZ. Illumination of FePTZ at 30 K results in a decrease of the ¹H NMR spin-lattice relaxation time T₁ due to formation of a high spin photoexcited state. The ¹H NMR of polystyrene containing a low concentration of FePTZ molecules shows a similar reduction in T₁, establishing that FePTZ can act as an optorelaxer for the protons of a matrix. Numerical modeling of the spin-diffusion processes from the protons in a FePTZ core to those in a shell of polystyrene accounts for the observed T₁ effects under both dark and light conditions. Additionally, ¹H MAS (magic-angle spinning) NMR results for pure FePTZ provide information on the isotropic and anisotropic portions of the electron-nuclear hyperfine interactions.     

Evaluation of diethylenetriaminepentaacetic acid-manganese(II) complexes modified by narrow molecular weight distribution of chitosan oligosaccharides as potential magnetic resonance imaging contrast agents

Novel conjugates of narrow molecular weight distribution of chitosan oligosaccharides (CSn; n=6, 8, 11) with manganese-diethylenetriaminepentaacetic acid (Mn-DTPA) as potential magnetic resonance imaging (MRI) contrast agents were synthesized. The structures were characterized by means of Fourier transform infrared spectra, ¹³C nuclear magnetic resonance, size exclusion chromatography and inductively coupled plasma atomic emission spectrometry. The characterization results showed that Mn-DTPA was successfully linked to aminated CSn by an amide function. The magnetic properties were characterized by in vitro and T₁-weighted FLASH image experiments. Relaxivities studies indicated that Mn-DTPA-CSn (n=8, 11) provided higher relaxivity, either in aqueous or bovine serum albumin solution (0.725 mM), than commercial contrast agent Gd-DTPA. The stability results showed that Mn-DTPA-CSn in aqueous were stable enough to prevent Mn^II ions from releasing. The preliminary in vitro and T₁-weighted FLASH image studies suggested that Mn-DTPA-CSn had the advantage of becoming promising MRI contrast agents.     

27Al Magic Angle Spinning Nuclear Magnetic Resonance Study of Al1−x Cr x K(SO4)2·12H2O (x = 0, 0.07, and 0.2)

The physical properties of Al_1?x Cr _x K(SO₄)₂·12H₂O (x = 0, 0.07, and 0.2) were studied as a function of temperature using magic angle spinning nuclear magnetic resonance for ²⁷Al. On the basis of the physical properties of pure AlK(SO₄)₂·12H₂O, the effects of partially replacing Al³⁺ with Cr³⁺ ions were examined. Molecular motion changed with the concentration of Cr³⁺ ions. The relaxation process near 320 K was found to undergo molecular motion as described by the Bloembergen–Purcell–Pound theory. The activation energies, phase transition temperatures, and spin–lattice relaxation times in the rotating frame T _1ρ changed with the concentration of paramagnetic ions.     

Metastatic Gastric Leiomyoblastoma: A Case Report

Gastric leiomyoblastoma is a rare entity. In this report, we describe the magnetic resonance (MR) appearance of a recurrent gastric leiomyoblastoma 14 years after initial presentation. This tumor was heterogeneous and moderately low signal intensity on T₁-weighted images and heterogeneous and moderately high signal intensity on T₂-weighted images. The tumor also contained foci of low signal intensity on the post gadolinium images, consistent with areas of necrosis. The mass enhanced mildly and increased in enhancement on the delayed images, consistent with a hypovascular mass. Multiple liver metastases were noted. Magnetic resonance findings were confirmed with surgical specimens.     

Effect of oxygen on the NMR relaxation properties of crude oils

Nuclear magnetic resonance relaxation measurements of bulk fluids provide a sensitive probe of the dynamics of molecular motion. Dissolved oxygen can interfere with this technique as its paramagnetic nature leads to a reduction of the paramagnetic relaxation times of the fluids. We studied this effect for the relaxation properties of crude oils that are in general characterized by a distribution of relaxation times. The samples were stock tank oils that have been exposed to air. We comparedT ₁ andT ₂ relaxation time distributions and their correlation functions of the initial (oxygenated) samples with those from the deoxygenated samples. Oxygen was removed from the oils with a freeze-thaw technique. As expected, the effect of oxygen is most apparent in oils with long relaxation times. In these oils the effect of oxygen can be described by an additional relaxation rate 1/T _1,2 ^ox to the transverse and longitudinal relaxation rates that is sample dependent but does not vary within the relaxation time distribution of the oil. Values of 1/T _1,2 ^ox for different crude oils were found to be in the range of 2.5 to 8.3 s. For crude oils that have components with relaxation times less than 100 ms, no significant oxygen effect is observed.     

19F Spin-lattice relaxation and stable radicals in radiation-modified fluoropolymers

Fluorine-19 spin-lattice relaxation of electron-beam-irradiated poly(tetrafluoroethylene) (PTFE) has been investigated in the temperature range from 250 to 315 K. As shown before, in the initial step, radicals are produced by the electron-beam irradiation and chain scission takes place. The concentrations of radicals and chain end groups after irradiation of PTFE strongly depend on the irradiation conditions. Radicals like other paramagnetic species decrease the spin-lattice relaxation times. In addition, decreased polymer chain lengths shift theT ₁ minimum to lower temperatures. Tetrafluorosuccinic acid in solution was used as a model system and paramagnetic copper sulphate CuSO₄ added to quantify the effect on the relaxation times. The shift of the minima inT ₁ versus temperature in PTFE are compared with the chain length determined from high-resolution solid-state nuclear magnetic resonance spectra and with the concentration of paramagnetic species.     

In vivo relaxation time measurements on a murine tumor model—Prolongation of T1 after photodynamic therapy

RIF tumors implanted on mice feet were investigated for changes in relaxation times (T₁ and T₂) after photodynamic therapy (PDT). Photodynamic therapy was performed using Photofrin II as the photosensitizer and laser light at 630 nm. A home-built proton solenoid coil in the balanced configuration was used to accommodate the tumors, and the relaxation times were measured before, immediately after, and up to several hours after therapy. Several control experiments were performed using the untreated tumors, tumors treated with Photofrin II alone, or tumors treated with laser light alone. Significant increases in T₁s of water protons were observed after PDT treatment. In all experiments, ³¹P spectra were recorded before and after the therapy to study the tumor status and to confirm the onset of PDT. These studies show significant prolongation of T₁s after the PDT treatment. The spin-spin relaxation measurements, on the other hand, did not show such prolongation in T₂ values after PDT treatment.