Control of susceptibility-related image contrast by spin-lock techniques

Macroscopic magnetic field inhomogeneities might lead to image distortions, while microscopic field inhomogeneities, due to susceptibility changes in tissues, cause spin dephasing and decreasing T₂ relaxation time. The latter effects are especially observed in the trabecular bone and in regions adjacent to air-containing cavities when gradient-echo sequences are applied. In conventional MRI, these susceptibility-related signal voids can be avoided by applying spin-echo (SE) techniques. In this study, an alternative method for the examination and control of susceptibility-related effects by spin-lock (SL) radiofrequency pulses is presented: SL pulses were applied in two different susceptibility-sensitive sequence types: (a) between the jump and return 90° pulses in a 90°_x−τ−90°_−x magnetization-prepared Fast Low Angle Shot (FLASH) sequence and (b) between the 90° pulse and the 180° pulse in an asymmetric SE sequence. The range of Larmor frequencies used for spin locking can be determined for different B₁ amplitudes of the SL pulses, allowing control of image contrast by the amplitude of the SL pulses.     

Time-Reverse ODESSA. A 1D Exchange Experiment for Rotating Solids with Several Groups of Equivalent Nuclei

A one-dimensional exchange experiment is proposed for magic-angle-spinning samples with several groups of equivalent nuclei undergoing internal exchange, such as pure reorientation, as opposed to mutual exchange. The method, which we term time-reverse ODESSA, is an extension of the recently proposed 1D ODESSA experiment for a single group of exchanging nuclei. When several different groups of spins are present, as is usually the case for carbon-13 in polymers and molecular crystals, the normal ODESSA spectrum yields phase-twisted spectra which are difficult to analyze quantitatively. This problem is solved in the time-reverse ODESSA experiment which yields pure absorption spectra for all families of side bands, as long as only internal exchange need be considered. The experiment consists of the usual three pulse sequence of 2D exchange,P1—t₁—P2—τ_m—P3—t₂(acquisition), except that the evolution time is fixed at half a rotation period,t₁= T_R/2, the mixing time is set to an odd number of half rotation periods, τ_m= (2G− 1)T_R/2, and the acquisition starts att₂= T_R/2 after the detection pulse,P3. The method is demonstrated using the carbon-13 spectra of dimethyl sulfone and an enriched sample of tropolone, and is applied to the study of the π flip of the inner benzene ring of 1,4-diphenoxybenzene. The scope and limitations of the method are discussed.     

Expanding the Frequency Range of the Solid-State T1 ρ Experiment for Heteronuclear Dipolar Relaxation

Solid-state spin–lattice relaxation in the rotating frame permits the investigation of dynamic processes with correlation times in the range of microseconds. The relaxation process in organic solids is driven by the fluctuation of the local magnetic field due to the dipole–dipole interaction of the probe nuclei (¹³C,¹⁵N) with ¹H in close proximity. However, its effect is often hidden by a competing relaxation process due to the contact between the rotating frame ¹³C/¹⁵N Zeeman and ¹H dipolar reservoirs. In most cases the latter process becomes superior for the commonly applied low and moderate spin-lock fields and practically does not provide information about the molecular dynamics. To suppress this undesired process and to expand the dynamic range of T_{1 ρ} experiments, we present two approaches. The first one uses a resonance offset of the frequency of the spin-lock irradiation, which leads to a significant enhancement of the effective spin-lock frequency without the application of destructive high transmitter powers. We derive the theory and demonstrate the applicability of the method on various model compounds. The second approach utilizes heteronuclear ¹H decoupling during the ¹³C/¹⁵N spin-lock irradiation which disrupts the contact between the ¹³C/¹⁵N Zeeman and ¹H dipolar reservoirs. We demonstrate the method and discuss the results qualitatively.     

7Li NMR analysis on perovskite structured Li0.15La0.28TaO3

The nanocrystalline perovskite material Li_0.15La_0.28TaO₃ has been synthesized by alkoxide-free Pechini type sol gel method. ⁷Li NMR measurements were carried out using a Bruker Avance 300 spectrometer at 116 MHz over the temperature range 150 to 400 K. Longitudinal spin-lattice relaxation times (T₁) measured by saturation recovery and longitudinal relaxation times in the rotating frame (T_1ρ) measured using the pulse sequence (π/2–spin lock τ acquisition) with lock radio-frequency field υ = 62.5 kHz and the T₂ relaxation time measured by Hahn echo are presented. The static Hahn-echo spectra show two different lithium sites in this perovskite oxide. Further, the relaxation measurements T₁ and T_1ρ show two different types of lithium cations with fast and slow dynamics.     

Determination of T1ρ values for head and neck tissues at 0.1 T: a comparison to T1 and T2 relaxation times

In order to optimize head and neck magnetic resonance (MR) imaging with the spin-lock (SL) technique, the T₁ρ relaxation times for normal tissues were determined. Furthermore, T₁ρ was compared to T₁ and T₂ relaxation times. Ten healthy volunteers were studied with a 0.1 T clinical MR imager. T₁ρ values were determined by first measuring the tissue signal intensities with different locking pulse durations (TL), and then by fitting the signal intensity values to the equation with the least-squares method. The T₁ρ relaxation times were shortest for the muscle and tongue, intermediate for lymphatic and parotid gland tissue and longest for fat. T₁ρ demonstrated statistically significant differences (p < 0.05) between all tissues, except between muscle and tongue. T₁ρ values measured at locking field strength (B1L) of 35 μT were close to T₂ values, the only exception being fat tissue, which showed T₁ρ values much longer than T₂ values. Determination of tissue relaxation times may be utilized to optimize image contrast, and also to achieve better tissue discrimination potential, by choosing appropriate imaging parameters for the head and neck spin-lock sequences.     

Analysis of inelastic scattering processes of electrons by localized electrons in quantum dots

The inelastic Coulomb scattering rate 1/τ_in of conduction electrons has been theoretically evaluated in the presence of localized states such as quantum dots. By a diagrammatical method, we have formulated 1/τ_in and its relation to the conductivity σ_loc(ω) through localized states. The dependence of τ_in on temperature T is examined in the case that σ_loc(ω) follows the Mott's model. It is found that 1/τ_in varies as T²(ln Δ/T)^d+1 where d is the dimensionality and Δ is tunneling energy between the localized states in the asymptonic T = 0 limit, in agreement with Imry's calculation. It is also found that calculated 1/τ_in deviates from T²(ln Δ/T)^d+1 as T increases, suggesting the importance of correction term at high temperature.     

Spectroscopy and dynamics of the excited singlet and triplet states of 2,3-, 2,4- and 2,5-difluorobenzaldehyde vapors

Emission and absorption spectra have been measured for 2,3-, 2,4- and 2,5-difluorobenzaldehyde vapors at different temperatures. The observed emission consists of the T₁(n, π*) phosphorescence accompanied by the weak S₁(n, π*) delayed fluorescence for all the molecules. The vibrational analyses of the emission spectra based on the results of the DFT calculations indicate that the observed emission originates from only the stable (anti) conformer. It is inferred from the temperature dependence of the phosphorescence intensity that the T₁(n, π*) → T₂(π, π*) internal conversion and/or the reverse T₁(n, π*) → S₁(n, π*) intersystem crossing contribute to the decrease in the phosphorescence intensity upon increasing temperature. The obtained spectroscopic data include the Raman spectrum of 2,3-difluorobenzaldehyde.     

Changes in electrical properties in α- and γ-exposed PADC track detector

The changes in the dielectric properties and temperature dependence of the d.c. conductivity of α-exposed poly allyl diglycol carbonate (PADC) have been studied. On α-irradiation the dielectric constant (′) as a function of frequency has been found to decrease significantly. The temperature dependence of resistivity in pristine and γ-irradiated samples is of the form ρ(T)=ρ_∝ exp(T₀/T) which can be attributed to conduction of thermally generated carriers. In case of (γ+α) irradiated samples the temperature dependence of resistivity is of the form ρ(T)=ρ_∝ exp(T₀/T)^1/2 which is due to one-dimensional hopping of carriers.     

A New Two-Dimensional Pulse Sequence for T2* Measurements of Protons in C Isotopomers

A new two-dimensional pulse sequence for T₂* measurement of protons directly coupled to ¹³C spins is proposed. The sequence measures the tranverse relaxation time of heteronuclear proton single-quantum coherence under conditions of free precession and is therefore well suited to evaluate relaxation losses of proton magnetization during preparation delays of heteronuclear pulse experiments in analytical NMR. The relevant part of the pulse sequence can be inserted as a “building block” into any direct or inverse detecting H,C correlation pulse sequence if proton spin–spin relaxation is to be investigated. In this contribution, the building block is inserted into a HETCOR as well as into a HMQC pulse sequence. Experimental results for the HETCOR-based sequence are given.     

T1ρ mapping improvement using stretched-type adiabatic locking pulses for assessment of human liver function at 3 T

PurposeThe purpose of this study is to investigate the performance of stretched-type adiabatic spin lock pulses for homogeneous spin locking with a flexible spin lock time (TSL) setting.MethodsT_1ρ values were obtained from 61 patients and five normal volunteers who were categorized using the Child–Pugh classification and scanned using each spin lock pulse type. The pulses used were the block and two kinds of hyperbolic secant (HS); HS8_10, and HS8_5. Visual scoring was categorized using a four point scale (1:Severe, 2:Moderate, 3:Mild and 4:None) to evaluate the homogeneity of the T_1ρ map and the source images obtained by each spin lock pulse. Mean T_1ρ values among the patient groups with different Child–Pugh classification were compared.ResultsThe visual assessment scores were 1.98 ± 1.05 for block pulse locking, 3.87 ± 0.39 for HS8_10 pulse locking, and 3.83 ± 0.45 for HS8_5 pulse locking, respectively. The scores between block pulse and HS8_10 were significantly different (p < 0.001), as were those between block pulse and HS8_5 (p < 0.001).The median T_1ρ values of normal liver function, Child–Pugh A, and Child–Pugh B or C were 37.00 ms, 40.77 ms, and 42.20 ms for block pulse, 46.75 ms, 50.78 ms, and 55.60 ms for HS8_10, and 48.80 ms, 55.42 ms, and 57.80 ms for HS8_5, respectively.ConclusionThe spin locking sequence using stretched-type adiabatic pulses provides homogeneous liver T_1ρ maps with reduced artifact and is necessary for a robust evaluation of liver function using T_1ρ.     

Phantom and in vivo study of the look–locher T1 mapping method

This paper describes and tests the LL-EPI method for obtaining quantitative T₁ estimates in a few seconds thereby allowing dynamic T₁ studies. It is shown that the method works even when there is an inflow into the imaged volume, e.g., in a vessel. No calibration is needed. The method has been tested in a phantom study with several different scan parameter set-ups, with and without inflow. The method shows robustness and individual scan parameters and inflow rates do not influence the ability to calculate the Gd-DTPA concentration. Linearity prevail between the measured 1/T₁ and the Gd-DTPA concentration in the range 150 < T₁ < 2500 ms. In a dynamic Gd-DTPA phantom study, it was shown that the dynamic LL-EPI T₁ mapping technique was three times more sensitive than the signal from a T^*₂-weighted EPI sequence. In an in vivo study, dynamic T₁ mapping of the Gd-DTPA uptake in a meningioma was performed. Inspection of the uptake curves indicates that the method is feasible in clinical perfusion studies.     

The measurement of R2, and R2′ in HIV-infected patients using the prime sequence as a measure of brain iron deposition

Brain iron deposition was assessed at 1.5 T in the caudate nucleus, globus pallidus and frontal and parietooccipital white matter in 28 human immunodeficiency virus (HIV)-infected patients and 15 control subjects with a new Partially Refocussed Interleaved Multi-Echo sequence by measuring 1/T₂, 1/T₂^* and 1/T2′ (i.e., R₂, and R₂′). There were significant differences in the R₂ and of the caudate nucleus (p < 0.0001 and p < 0.05) and the R₂, and R₂′ of the globus pallidus (p < 0.001, p < 0.005 and p < 0.05) in HIV-infected patients compared to control subjects. There was a trend for higher values of R₂, and R₂′ in the globus pallidus and caudate nucleus in HIV-infected patients with later stage HIV disease. These results suggest that there is greater iron deposition in the basal ganglia of HIV-infected patients compared with control subjects, with a predilection for the globus pallidus. The relationship between iron deposition in the brain and various parameters of severity of HIV infection remains uncertain.     

Improved Estimation of Protein Rotational Correlation Times fromN Relaxation Measurements

In the study of protein backbone dynamics by¹⁵N relaxation measurements, an initial estimation of the isotropic global correlation time, τ_m, is usually obtained from the averageT₁/T₂ratio of nuclear spins that do not exhibit slow internal motion and withT₂values not significantly shortened by chemical or conformational exchange processes. Different methods have been used for identification of the rates of internal motion. However, the number of nuclear spins included in the τ_mestimation is often larger than the number that ultimately can be fitted to a single-order parameter,S², implying that some nuclear spins involved in the initial τ_mestimation actually have an effective internal correlation time, τ_e, not as fast as assumed. As a consequence, τ_mis underestimated, since internal motion reduces theT₁/T₂ratio. This situation becomes more obvious if the molecule has a large τ_mvalue because the reduction inT₁/T₂ratio arising from internal motion is more significant than for molecules with smaller τ_mand the same degree of internal motion. This Communication describes a more reliable method for identifying nuclear spins which should be excluded from the τ_mestimation because of insufficiently rapid internal motion. This results in an improved τ_mvalue, giving a much better agreement between the number of nuclear spins fitted successfully to a single-order parameter,S², and those used in the τ_mestimation.     

An analysis of DC conductivity in terms of degradation mechanisms induced by thermal aging in polypyrrole/polyaniline blends

Measurements of the d.c. electrical conductivity on thermally treated polypyrrole/polyaniline (PPy/PANI) samples, in which the PPy content increased by 10% w.w. starting from pure PANI to pure PPy, followed a σ(t, T) = σ₀(t)exp[−(T₀/T)^1/2] law. This is consistent with a heterogeneous structure of the granular metal type, in which aging is accompanied by the shrinking of the conductive grains causing the decrease of the sample conductivity, a process which is described by the increase of the parameter T₀. The preexponential factor σ₀(t) depends on the intrinsic conductivity of the grains and geometrical factors affecting the carrier paths through the energy barriers, as are the grain size distribution and the mean volume occupied by the conducting grains in the material. It was found that for the samples as a whole the thermal aging law, which predicts ln σ(t, T)∝t^1/2 is followed for a given temperature T, where t is the time of the thermal treatment, in accordance with a granular metal type structure. On the other hand, the preexponential factor σ₀(t) decreases with the aging, following a different law [σ(t = 0, T)−σ(t, T)]/σ(t = 0, T)∝t^1/2, where σ(t = 0, T) is the initial value of σ₀(t), that of the fresh sample. This law reveals an aging caused by a degradation proceeding into the interior of the grains in a diffusion-like manner. So, the two different laws of aging, one from T₀ and the other from σ₀, reveal that the aging does not simply reduce the size of the grains, but affects their interior, this degradation decreases with depth.     

Physical processes of current gain in InAs bipolar junction transistors

InAs bipolar junction transistors (BJTs), grown by molecular beam epitaxy, are reported with common emitter current gains (β's) as large as 400. The factors affecting the common emitter current gain have been studied by estimating the magnitudes of the base transport factor (α_T) and emitter injection efficiency (γ). This has been accomplished by studying a sequence of InAs BJTs with varying emitter doping densities, N_E. Minority carrier diffusion length in the base (L_B), α_T, and γ have been extracted from measured electrical characteristics. The results of the study of these InAs BJTs are as follows: L_B≈0.4 μm, α_T≈98% and γ ranges from 92% to nearly 100% depending on N_E. This knowledge of the magnitudes of the injection efficiencies suggests when it would be useful to move from the simple BJT structure to the more advanced heterojunction bipolar transistor (HBT) structure. Lower γ BJTs would be improved, however high-γ BJTs would benefit little, by the use of the widegap emitters of HBTs. The method developed here to estimate γ, α_T and L_B is not specific to InAs BJTs, but should be useful for study of BJTs and HBTs in any material system.     

Phase transition of directed polymer in random potentials on 4+1 dimensions

Finite-temperature-directed polymer in random potentials is described by a transfer matrix method. On 4+1 dimensions, the evidence for a finite-temperature phase transition is found at T_c≈0.18, where the free energy fluctuation grows logarithmically as a function of time t. When TT_c, the fluctuation of the free energy grows as t^ω with ω≈0.156. The phase transition of the restricted solid-on-solid model, which is closely related to the directed polymer problem through the Kardar–Parisi–Zhang equation, is also discussed.     

Studies of the quantum Hall to quantum Hall insulator transition in InSb-based 2DESs

The temperature dependence of ρ_xx is studied in the vicinity of the quantum Hall to quantum Hall insulator transition (ν=1→0) in InSb/InAlSb based 2DESs. ρ_xx displays a symmetric temperature dependence about the transition with on the QH side and on the insulating side. A plot of 1/T₀ for successive ν displays power-law divergence with 1/T₀∝|ν−ν_c|^−γ,² with γ=2.2±0.3. This critical behavior in addition to the behavior expected of the quantum transport regime confirms that the QH/QHI transition is indeed a good quantum phase transition.     

The emission spectrum of the diatomic radical, phosphorus selenide

The emission spectrum of the PSe radical is reported for the first time. Seventy-eight reddegraded bands in the region 4000–6500 Å have been measured and assigned to the A²Π-X²Π transition of PSe. Isotope shifts observed for some bandheads have been utilized in deriving the vibrational numbering. The molecular constants have been determined as (in units of cm⁻¹): ω′ = 406.9, ω′_eχ′_e = 1.3, ω″ = 556.9, ω″_eχ″_e = 1.3, and T_e = 19477.3 for the ²Π_1/2 states; and ω′_e = 402.4, ω′_eχ′_e = 1.5, ω″_e = 556.8, ω″_eχ″_e = 1.6, and T_e = 19178.0 for the ²Π_3/2 states.