Dextran‐Coated Antiferromagnetic MnO Nanoparticles for a T1‐MRI Contrast Agent with High Colloidal Stability

A simple approach to synthesize carboxymethyl dextran‐coated MnO nanoparticles (CMDex‐MnONPs) with high colloidal stability in physiological saline solutions is described here for potential applications as a magnetic resonance imaging (MRI) T₁ contrast agent. The thermal decomposition methodology is used to produce uniform MnONPs with an average size of around 20 nm, and its hydrophobic surface is modified with CMDex molecules, conferring hydrophilic properties. After CMDex coating, the nanoparticle presents high colloidal stability in concentrations ranging from 10 to 50 μg mL^?1, average hydrodynamic size (Z‐average) of 130 nm, polydispersity degree of ≈12%, and negative surface charge in both simulated body fluid solutions and pure water with zeta‐potential of –20 and –40 mV, respectively. The CMDex‐MnONPs with 20 nm show antiferromagnetic behavior at room temperature, and the magnetic properties are found to be strongly dependent of the nanoparticle size, increasing the contribution of the ferromagnetic Mn₃O₄ phase with decreasing size for nanoparticles about 3 nm. Cytotoxicity evaluation in cancerous and noncancerous cells in the range of 5.0–50.0 μg mL^?1 shows low toxicity for cancerous cells and lack of the same for healthy cells lines. Related to the magnetic properties, CMDex‐MnONP presents significant r₁ relaxivity and low r₂/r₁ relaxivity ratio. The results suggest that these nanoparticles display characteristics for potential applications as an MRI T₁ contrast agent.     

Practical considerations in T1 mapping of prostate for dynamic contrast enhancement pharmacokinetic analyses

There are many challenges in developing robust imaging biomarkers that can be reliably applied in a clinical trial setting. In the case of dynamic contrast-enhanced (DCE) MRI, one such challenge is to obtain accurate precontrast T₁ maps for subsequent use in two-compartment pharmacokinetic models commonly used to fit the MR enhancement time courses. In the prostate, a convenient and common approach for this task has been to use the same 3D spoiled gradient-echo sequence used to collect the DCE data, but with variable flip angles (VFAs) to collect data suitable for T₁ mapping prior to contrast injection. However, inhomogeneous radiofrequency conditions within the prostate have been found to adversely affect the accuracy of this technique. Herein we demonstrate the sensitivity of DCE pharmacokinetic parameters to precontrast T₁ values and examine methods to improve the accuracy of T₁ mapping with flip angle-corrected VFA SPGR methods, comparing T₁ maps from such methods with “gold standard” reference T₁ maps generated with saturation recovery experiments performed with fast spin-echo (FSE) sequences.     

Oxygen defects relaxation in high-temperature YBa2Cu3O7 superconductors

The temperature dependences of normal state static magnet susceptibility χ(T) for high-temperature YBa₂Cu₃O₇ superconductors (T _c ≤ T ≤ 400 K) measured for the same sample before and after 22 years of storage are compared. It is shown that during longime storage of a maximally doped sample, its electronic system is more in equilibrium than it was in the initial state, while a similar underdoped sample decomposed completely. Comparing the χ(T) curves for YBa₂Cu₃O₇, we draw conclusions as to the nature of the Curie contribution and the fluctuation-induced contribution to the magnetic susceptibility of the investigated sample, and the experimental procedure for determining T _c.     

Amphiphilic Core–Shell Nanocomposite Particles for Enhanced Magnetic Resonance Imaging

A scalable synthesis of magnetic core–shell nanocomposite particles, acting as a novel class of magnetic resonance (MR) contrast agents, has been developed. Each nanocomposite particle consists of a biocompatible chitosan shell and a poly(methyl methacrylate) (PMMA) core where multiple aggregated γ‐Fe₂O₃ nanoparticles are confined within the hydrophobic core. Properties of the nanocomposite particles including their chemical structure, particle size, size distribution, and morphology, as well as crystallinity of the magnetic nanoparticles and magnetic properties were systematically characterized. Their potential application as an MR contrast agent has been evaluated. Results show that the nanocomposite particles have good stability in biological media and very low cytotoxicity in both L929 mouse fibroblasts (normal cells) and HeLa cells (cervical cancer cells). They also exhibited excellent MR imaging performance with a T₂ relaxivity of up to 364 mM_Fe^?1 s^?1. An in vivo MR test performed on a naked mouse bearing breast tumor indicates that the nanocomposite particles can localize in both normal liver and tumor tissues. These results suggest that the magnetic core–shell nanocomposite particles are an efficient, inexpensive and safe T₂‐weighted MR contrast agent for both liver and tumor MR imaging in cancer therapy.     

Fast chemical-shiftT 1 imaging in toroid cavities for the structural analysis of gels and emulsions

Fast chemical-shiftT ₁ imaging in toroid cavity cells (TCCs) is introduced and applications to diagnostic ultrasound gel and skin-care ointment are presented. TCCs are an advancement over previously used toroid cavity detectors because they combine resonator and sample container into one part. Additionally, they are removable from the top of the probe and facilitate convenient probe and sample handling. Radially resolvedT ₁ relaxation times in TCCs are obtained through combination of SR (saturation recovery) experiments with the RIPT (rapid imaging with a pulse train) technique. Because of the strong radialB ₁ gradient in TCCs, only pulse-burst saturation was found satisfactory to generate the most even starting condition for SR experiments. Because RIPT does not resolve chemical-shift information, magnetization andT ₁ profiles of individual components in mixed samples are monitored by double-transient experiments with selective on-resonance saturation, which is achieved by converging trains of sinc pulses. The new techniques were applied to cellulose hydrogel and oil-in-water emulsion both exposed to significant shear stress deformation during the charging of the TCC. In both cases,T ₁ profiles as a function of time reveal structural recovery (thixotropy) that slowly progresses from one or more sample interfaces into the bulk.     

Imaging Perfusion Deficits in Ischemic Heart Disease with Susceptibility-Enhanced T2-Weighted MRI: Preliminary Human Studies

Aim: This feasibility study explores relative myocardial perfusion characterization with an investigational T₂/T₂1 contrast agent. Methods: Dysprosium-DTPA bis (methylamide) was administered peripherally in six patients with thallium defects. Rest and stress multi-section, gated, T₂-weighted images were acquired with a 1.5 T echo-planar imager. Change in transverse relaxation rate was calculated in four segments for each subject. Results: Magnetic resonance (MR) identified five of five instances of ischemia or infarction, at a dose of agent (0.25 mmol/kg) that was comparable to that currently used with clinically approved gadolinium agents. Injection at twice this dose resulted in saturation of the signal change, and the one ischemic segment corresponding to the higher dose was not identified by MR. MR was negative in two segments which, on final diagnosis, were determined to manifest thallium attenuation artifact. Conclusion: MR perfusion imaging with high susceptibility agents has the potential to characterize myocardial perfusion deficits.     

Effects of Fe doping on ac susceptibility of Pr0.75Na0.25MnO3

Ac susceptibility at low temperatures of Pr_0.75Na_0.25Mn_1-xFe_xO₃ (0 ≤ x ≤ 0.30) is investigated. The peak value of the real component of ac susceptibility χ' at the freezing temperature T_f is suppressed with the increasing frequency. The peak value of χ' shows a linear relation between T_f and the logarithm of the frequency ω. The normalized slope P = ΔT_f/T_fΔlgω, which is much lower than canonical insulating spin glass systems in which 0.06 ≤ P ≤ 0.08. The peak value of the imaginary component of the ac susceptibility χ' at T_f for the x = 0, 0.02, 0.30 samples increases with increasing frequency, suggesting a cluster glass ground state with a coexistence of charge-ordered phase and correlated ferromagnetic clusters in spin glass matrix. The peak value of χ' at T_f for the x = 0.10 sample decreases with increasing frequency, suggesting a phase separation ground state. The peak value of χ' at T_f for the x = 0.05 sample decreases with increasing frequency for ω ≤ 52 Hz and increases subsequently till 701 Hz, and then decreases with further increasing frequency for ω ≥ 1501 Hz. This complex behaviour is ascribed to the competition between the effects of large and little ferromagnetic clusters in the sample. The ground state of x = 0.05 sample is a transition state from cluster glass to phase separation.     

Magnetic properties of PrCo2 and its ternary hydride PrCo2H4

Magnetization and susceptibility data on PrCo₂ and PrCo₂H₄ are presented. The ac susceptibility of PrCo₂ measured in zero dc field displays a sharp and high peak at T_c = (39.9 ± 0.2) K. The magnetization versus temperature curves show ferromagnetic behaviour for B >1 T, but display a maximum at lower values of the applied field. These results, together with the behaviour of the hysteresis loops at different temperatures below T_c, indicate that PrCo₂ orders ferromagnetically, the magnetic hardness increasing strongly for T → 0. The saturation moment at 4.2 K equals 3.9 μ_B per formula unit, as found from the magnetization curve measured in a pulsed-field magnet up to B = 30 T.Similar experiments on PrCo₂H₄ provide evidence that the introduction of hydrogen in PrCo₂ not only destroys the long-range atomic order, but also considerably reduces the ferromagnetic interactions. Such an effect of the hydrogen is commonly observed in cobalt intermetallics. Part of the PrCo₂H₄ is found to have decomposed into PrH₂ and free Co. The clusters of free Co atoms give rise to a maximum in the zero-field ac susceptibility versus temperature curves, similar as observed in spin glasses or magnetic glasses. By increasing the ac frequency, the maximum shifts to higher temperatures. The behavior can be explained in terms of the Néel model for superparamagnetic particles with randomly oriented local anisotropy axes.     

Dispersion of cerebral on-resonanceT 1 in the rotating frame (T 1ρ) in global ischaemia

T ₁ in the rotating frame (T _1ρ) has been recently shown to be an early magnetic resonance imaging index of ongoing pathology in vivo. Dispersion ofT _1ρ at aB ₁ range from 620 to 160500 rad/s was quantified in the rat brain to study the effects of ischaemia onT _1ρ relaxation and to elude the role of physico-chemical mechanisms underlying the relaxation changes. The results show a biphasic effect of the dispersion ofR _1ρ (1/T _1ρ) in ischaemic brain. In the lowB ₁ region (less than 5000 rad/s), an increase was detected, while at the highB ₁ end of the experiments,R _1ρ was reduced. This was accompanied by a change in the fitted values describing the dispersion characteristics. Injection of a superparamagnetic contrast agent, AMI-227, before ischaemia shifted theR _1ρ curve upwards by 4% but showed no effect on the shape of theR _1ρ dispersion curve. The present results argue for a specific effect of endogenous susceptibility on cerebralR _1ρ in the early moments of ischaemia due to a relaxation enhancement in the blood pool. Our results confirm that quantitativeR _1ρ dispersion nuclear magnetic resonance (NMR) improves the sensitivity ofR _1ρ NMR to detect ischaemia in vivo. Simple empirical linear or exponential fits proved to be efficient ways to describe dispersion data in the limitedB ₁ range, as more detailed models may not offer additional information in a physically relevant manner for complex systems, such as the brain.     

Unconventional antiferromagnetic correlations of the doped Haldane gapsystem Y 2 BaNi 1 - x Zn x O 5

We make a new proposal to describe the very low temperature susceptibility of the doped Haldane gap compound Y₂BaNi_1-xZn_xO₅. We propose a new mean field model relevant for this compound. The ground state of this mean field model is unconventional because antiferromagnetism coexists with random dimers. We present new susceptibility experiments at very low temperature. We obtain a Curie-Weiss susceptibility χ( T ) ∼ C /(Θ + T ) as expected for antiferromagnetic correlations but we do not obtain a direct signature of antiferromagnetic long range order. We explain how to obtain the “impurity” susceptibility ( T ) by subtracting the Haldane gap contribution to the total susceptibility. In the temperature range [1 K, 300 K] the experimental data are well fitted by T ( T ) = C _imp 1 + T _imp / T . In the temperature range [100 mK, 1 K] the experimental data are well fitted by T ( T ) = A ln( T / T _c ), where T _c increases with x. This fit suggests the existence of a finite Néel temperature which is however too small to be probed directly in our experiments. We also obtain a maximum in the temperature dependence of the ac-susceptibility ( T ) which suggests the existence of antiferromagnetic correlations at very low temperature. Received 17 July 2001     

混沌系统平均初始误差增长饱和特性研究

在非线性误差增长理论框架下研究了混沌系统平均初始误差增长饱和特性 以及误差饱和值同系统可预报期限的关系.首先探索了Lorenz96系统中平均相对初始误差增长饱和规律, 发现平均相对初始误差增长饱和值同初始误差的自然对数存在简单的线性关系: 其二者自然对数之和为一常量,且该常量同初始误差无关.实验表明该结论对其他混沌系统也适用. 因此对给定混沌系统,在计算出和常数后可以外推得到任意固定初始误差的平均相对误差增长饱和值. 为进一步研究误差饱和值同可预报期限的关系,给出了平均绝对误差增长的定义. 理论分析表明混沌系统平均绝对误差增长也会达到饱和.其饱和值为常量, 与初始误差无关,混沌系统控制参数确定,饱和值就固定.依据上述研究, 最后给出一个定量计算可预报期限的模型T_p=1/∧ln(E_s/δ₀)+c, E_s为绝对误差增长饱和值.实验研究表明对于复杂的高阶混沌系统,该预报期限模型都能较好地适用.     

Measurement of APT using a combined CERT-AREX approach with varying duty cycles

The goal is to develop an imaging method where contrast reflects amide-water magnetization exchange, with minimal signal contributions from other sources. Conventional chemical exchange saturation transfer (CEST) imaging of amides (often called amide proton transfer, or APT, and quantified by the metric MTR_asym) is confounded by several factors unrelated to amides, such as aliphatic protons, water relaxation, and macromolecular magnetization transfer. In this work, we examined the effects of combining our previous chemical exchange rotation (CERT) approach with the non-linear AREX method while using different duty cycles (DC) for the label and reference scans. The dependencies of this approach, named AREX_double,vdc, on tissue parameters, including T₁, T₂, semi-solid component concentration (f_m), relayed nuclear Overhauser enhancement (rNOE), and nearby amines, were studied through numerical simulations and control sample experiments at 9.4 T and 1 μT irradiation. Simulations and experiments show that AREX_double,vdc is sensitive to amide-water exchange effects, but is relatively insensitive to T₁, T₂, f_m, nearby amine, and distant aliphatic protons, while the conventional metric MTR_asym, as well as several other APT imaging methods, are significantly affected by at least some of these confounding factors.     

Spin glass like behavior in Cd0.42Mn0.58In2S4

The magnetic behavior of the diluted magnetic semiconductor Cd_0.42Mn_0.58In₂S₄ has been study by dc magnetization and ac susceptibility experiments. Zero field cooled and field cooled measurements reveal irreversibility below T_irr=2.60±0.15 K. Ac susceptibility data, performed as a function of the temperature and the frequency, confirm the spin-glass like behavior of the material with T_f=2.75±0.15 K. High temperature susceptibility data follow a typical Curie-Weiss law with θ=−74±1 K which suggests predominant antiferromagnetic interactions. The randomness of the magnetic ions, necessary to explain the magnetic behavior of the material, has been determined by X-ray powder diffraction experiments.     

A statistical fMRI model for differential T2* contrast incorporating T1 and T2* of gray matter

Relaxation parameter estimation and brain activation detection are two main areas of study in magnetic resonance imaging (MRI) and functional magnetic resonance imaging (fMRI). Relaxation parameters can be used to distinguish voxels containing different types of tissue whereas activation determines voxels that are associated with neuronal activity. In fMRI, the standard practice has been to discard the first scans to avoid magnetic saturation effects. However, these first images have important information on the MR relaxivities for the type of tissue contained in voxels, which could provide pathological tissue discrimination. It is also well-known that the voxels located in gray matter (GM) contain neurons that are to be active while the subject is performing a task. As such, GM MR relaxivities can be incorporated into a statistical model in order to better detect brain activation. Moreover, although the MR magnetization physically depends on tissue and imaging parameters in a nonlinear fashion, a linear model is what is conventionally used in fMRI activation studies. In this study, we develop a statistical fMRI model for Differential T₂^? ConTrast Incorporating T₁ and T₂^? of GM, so-called DeTeCT-ING Model, that considers the physical magnetization equation to model MR magnetization; uses complex-valued time courses to estimate T₁ and T₂^? for each voxel; then incorporates gray matter MR relaxivities into the statistical model in order to better detect brain activation, all from a single pulse sequence by utilizing the first scans.     

Three-dimensional T1, T2 and proton density mapping with inversion recovery balanced SSFP

By combining a balanced steady-state free precession (bSSFP) readout with an initial inversion pulse, all three contrast parameters, T₁, T₂ and proton density (M₀), may be rapidly calculated from the signal progression in time. However, here it is shown that this technique is quite sensitive to variation in the applied transmit RF (B₁) field, leading to pronounced errors in calculated values. Two-dimensional (2D) acquisitions are taxed to accurately quantify the relaxation, as the short RF pulses required by SSFP's rapid TR contain a broad spectrum of excitation angles. A 3D excitation using a large diameter excitation coil was able to correctly quantify the parameters. While the extreme B₁ sensitivity was previously problematic and has precluded use of IR-bSSFP for relaxometry, in this work these obstacles were significantly reduced, allowing the rapid quantification of T₁, T₂ and M₀. The results may further be used to simulate image contrast from common sequences, such as a T₁-weighted or fluid-attenuated inversion recovery (FLAIR) examination.     

Superconductivity in the hole-doped oxy-arsenide RE1−xSrxFeAsO (RE = La, Pr)

Bulk superconductivity was observed in the FeAs-based RE_1−xSr_xFeAsO (RE = La, Pr) when the di-valence element Sr was substituted to the site of the tri-valence element La and Pr. The maximum superconducting transition temperatures T_c for the two systems are 26 K and 16.3 K, respectively. The doping dependence of the electrical properties and structure of these two systems were investigated systematically. A roughly monotonic increase of T_c and the lattice constants (a-axis and c-axis) with Sr concentration and a saturation behavior in the high doping levels were found. We confirmed that conduction in this type of materials is dominated by hole-like charge carriers by the Hall effect measurements. Also the resistive measurements revealed possible higher upper critical field in these systems comparing with the electron-doped ones.     

Nouvelles donnes experimentales sur les proprietes magnetiques de Cr3 Se4 et des solutions solides Cr3 Set S4−t

Magnetic susceptibility and specific heat measurements and neutron diffraction experiments allow to locate Néel temperatures T_N and also two types of transitions below T_N. At T_t of order T_N/2 the susceptibility is maximum, and the magnetic structure is modified (for Se-rich compounds). The second transition takes place around 15 K and is characterized by a specific heat peak and a susceptibility anomaly but no modification of the magnetic structure, according to our powder diffraction data.     

Electron transport properties of Co71−xFexCr7Si8B14 (x=0, 2, 3.2, 4, 6,8 and 12 at%) amorphous alloys during devitrification

The investigation addresses the electron transport properties of Co_71−xFe_xCr₇Si₈B₁₄ (x=0, 2, 3.2, 4, 6, 8 and 12 at%) amorphous alloys. The variation in electrical resistivity of as-cast amorphous materials with thermal scanning from room temperature to 1000 K was measured. The CoFe-based alloys revealed an initial decrease in temperature coefficient of resistivity (TCR), a characteristic of spin-wave phenomena in glassy metallic systems. This behaviour in the present alloys was in a sharp contrast to the Co-based amorphous materials that indicate the drop in resistivity much below room temperature. In the studied alloys, the variation in initial TCR values and the full-width at half-maxima determined from X-ray diffraction of as-quenched materials exhibited a similar trend with increasing Fe content, indicating the compositional effect of near neighbouring atoms. After the initial decrease in resistivity, all the alloys indicated a subsequent increase at T_min. The Curie temperature (T_C), which was measured from thermal variation of ac susceptibility showed non-monotonic change with Fe content. In the temperature range between T_min and T_C the relative scattering by electron-magnon and electron-phonon resulted in the non-monotonic change in Curie temperature. At crystallization onset (T_X1) all the alloys except there with X=6, showed a sharp decrease in electrical resistivity which was attributed to ordering phenomena. In contrast to this resistivity decrease, X=6 alloy exhibited a drastic increase in resistivity around T_X1 observed during amorphous to nanocrystalline transformation. Such nanocrystalline state was observed by Transmission electron microscopy.     

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.     

Specific heat of the non-centrosymmetric superconductor Re3W

The alloys of non-centrosymmetric superconductor, Re 3 W, which were reported to have an α-Mn structure [P. Greenfield and P. A. Beck, J. Metals, N. Y. 8, 265 (1959)] with T c = 9 K, are prepared by arc melting. The values of ac susceptibility and the low-temperature specific heat of these alloys are measured. It is found that there are two superconducting phases coexisting in the samples with T c1 ≈ 9 K and T c2 ≈ 7 K, which are both non-centrosymmetric in structure as reported previously. By analysing the specific heat data measured in various magnetic fields down to a temperature of 1.8 K, we find that the absence of the inversion symmetry does not lead to an obvious deviation from an s-wave pairing symmetry in Re 3 W.