Molecular dynamics in solid riboflavin as studied by 1H NMR

Spin–lattice relaxation times T₁ and T_1d as well as NMR second moment were employed to study the molecular dynamics of riboflavin (vitamin B₂) in the temperature range 55–350 K. The broad and flat T₁ minimum observed at low temperatures is attributed to the motion of two nonequivalent methyl groups. The motion of the methyl groups is interpreted in terms of Haupt's theory, which takes into account the tunneling assisted relaxation. An additional mechanism of relaxation in the high temperature region is provided by the motion of a proton in one of the hydroxyl groups. The Davidson–Cole distribution of correlation times for this motion is assumed.     

基于多弛豫信号补偿的快速磁共振T1ρ散布成像

定量磁共振成像（MRI）可量化组织特性,是科学研究和临床研究的重要工具.旋转坐标系下的自旋-晶格弛豫时间（T_1ρ）能反映水与大分子之间的低频交互作用,在3 T及以上的高场环境下,T_1ρ受水和不稳定质子之间化学交换的影响较大,通过测量弛豫率随自旋锁定场强度的变化而得到其分布情况（T_1ρ散布）,可用于分析和量化质子的交换过程,因此T_1ρ散布是一种重要的定量MRI技术.然而,获得不同自旋锁定场强下T_1ρ加权图像的时间过长,限制了其应用范围.针对这一问题,本研究提出一种基于多弛豫信号补偿策略的快速T_1ρ散布成像方法.该方法将不同锁定频率下的T_1ρ加权图像补偿到同一信号强度水平,并结合低秩与稀疏建立重建模型.实验结果表明,该方法在加速倍数高达7倍时仍获得了较好的重建结果.     

Molecular dynamics of polycrystalline cellobiose studied by solid-state NMR

Molecular motions of polycrystalline cellobiose have been investigated by measuring proton spin–lattice relaxation times, T₁ and T_1ρ, and the second moment, M₂, in both protonated and D₂O exchanged forms over the temperature range 120–380 K. T₁ relaxation is dominated by the motions of hydroxyl groups between 150 and 380 K, characterised by an activation energy of about 8.74 kJ/mol, whereas T_1ρ relaxation is driven by the motions of the same groups between 120 and 300 K. T_1ρ results suggest that hydroxyl groups have a distribution of dynamics. Motion of methylene groups was detected in the second-moment experiments at about 350 K, characterised by activation energy of about 40 kJ/mol. Consideration of the calculated and observed rigid-lattice second moments suggests that the reported X-ray data are incorrect for the inter-proton distance on C6′. ¹³C CPMAS spectra of both protonated and deuterated cellobiose have also been measured. Spectra of the deuterated material showed the existence of a second crystalline form in addition to the normal form.     

Visualization of residual anisotropic interactions in crosslinked natural rubbers by dipolar local field measurements and H natural abundance NMR spectroscopy

An extension of the exploitation of indirect observation of ¹H nuclei through ¹³C resonances is presented in the case of crosslinked elastomers. It is demonstrated that, by using this method in vulcanized elastomers above T_g a direct visualization of residual dipolar interactions on different functional groups as well as their dependence on motional constraints is available. It is also shown that ²H natural abundance NMR spectra of elastomers provide similar information on motional constraints by way of residual quadrupolar interactions.     

Solid-state 13C NMR study of poly(vinyl alcohol) gels

Poly(vinyl alcohol) (PVA) with 55% and 61% syndiotacticity, and their related dry and hydrated gels obtained by two different freeze–thawing cycles have been investigated using the solid-state ¹³C CP-MAS NMR technique. From a comparative analysis of the spectra, evidence was obtained that the gelation process largely disrupts the intramolecular hydrogen-bonded network of the PVA. The addition of water to the dry gels favours their swelling, destroying intra-chain hydrogen bonds between hydroxyl groups as a function of the degree of tacticity and the gelation procedure, and promotes the formation of new networks of interchain hydrogen bonds. Information on the dynamics of the polymeric domains in the kilohertz range has been obtained from the analysis of the spin relaxation times T_1ρ(¹H) and T_1ρ(¹³C), indicating that homogeneous arrangements of the amorphous or swollen polymeric chains exist, independent of the preparation method or the tacticity of the PVA chains.     

Longitudinal nuclear relaxation measurements in hcp H2

Measurements of T₁ in the hep phase of H₂, over the temperature range 2°–12°K and the ortho concentration range between 0.5 and 0.97 are presented. At temperatures below 10°K, the thermally activated self-diffusion is negligible and the mechanism for nuclear relaxation is that attributed by Moryia and Motizuki and by Harris to intramolecular dipolar interaction, modulated by intennolecular electric quadrupole-quadrupole (EQQ) interaction. The gaussian approximation for the correlation function was used by these authors to predict T₁. From the comparison between experiment and theory, we determine the EQQ parameter Γ/k_B to be 0.67°K. Above 10°K the effect of diffusion influences T₁, and the experimental results for an 88 per cent ortho H₂ sample up to the melting point suggest that the relaxation mechanisms resulting from EQQ interaction and diffusion are not independent of one another.     

固体核磁共振研究半晶聚-3-羟基丁酸酯和聚羟基丁酸戊酸酯的分子动力学

本文在150~370 K温度范围内,采用固体核磁共振（NMR）测定了半晶聚-3-羟基丁酸酯（PHB）,以及3-羟基戊酸酯单体质量分数分别为5%（PHBV5）和12%（PHBV12）的聚羟基丁酸戊酸酯共聚物在实验室坐标系和旋转坐标系条件下质子的自旋-晶格弛豫时间T₁和T_1ρ.通过弛豫时间随温度变化的理论拟合,分别获得上述半晶聚合物晶区和结晶区的分子动力学参数（包括E_a和τ₀）.这些结果从分子水平上阐述了PHB结构修饰和增强的原因.     

Temperature range for critical scaling behavior in YBCO thin films

The magnetic and transport properties of thin films and single crystals of YBa₂Cu₃O_7−δ are compared. For measurements on thin films, the apparent critical scaling behavior is observed to exist over a temperature range from 87 K down to the vortex-glass transition T_g = 84.2 K at 2.5 kOE and from 83 K to T_g = 70.4 K at 50 kOe. The inflection point (T_inf) in temperature dependent resistivity measurements R(T) coincides with the highest temperature at which current-voltage (I–V) characteristics are found to scale. The region between T_g and T_inf shows a behavior characteristics of thermally activated flux motion, while above T_inf I–V curves show ohmic behavior. No similar scaling region is observed in some single crystal results, supporting recent claims that the phase transition in some single crystals may not be critical in nature (of order greater than one).     

Myocardial proton spin-lattice relaxation times in vitro: Effect of elapsed time after excision

An assumption made in using excised tissue for in vitro nuclear magnetic resonance (NMR) studies is that variables of interest, such as spin-lattice (T₁) relaxation times, remain stable for periods of time after excision sufficient to perform NMR spectroscopy. In this study, we evaluated the changes in T₁ of rat myocardium, measured at two NMR field strengths, at serial time intervals up to 72 hours postmortem. Left ventricular myocardium from six male Sprague-Dawley rats was excised and stored at room temperature in sealed NMR sample tubes. Spin-lattice relaxation times were determined with a modified inversion-recovery pulse sequence immediately postmortem and at intervals up to 72 hours post-excision; NMR studies were performed using 90 MHz and 360 MHz spectrometers. A gradual decrease in T₁ was noted with increasing time post-excision; T₁ was not significantly shorter than baseline until 72 hours postmortem at either field strength. The rate of change of T₁ was similar at the two field strengths. At any given time post-excision, T₁ was significantly higher (p < 0.001) at 360 MHz than at 90 MHz. We conclude that, with proper tissue handling and storage techniques, rat myocardial T₁ is stable postmortem sufficiently long to permit meaningful NMR studies of excised tissue.     

Spin fluctuations in weakly itinerant ferromagnets Y(Co1−xAlx)2

The nuclear spin-lattice relaxation rate, 1/T₁, has been measured in weak itinerant ferromagnets Y(Co_1−xAl_x)₂. The temperature and magnetic field dependence of 1/T₁T has been found to be well described by the self-consistent renormalization (SCR) theory of spin fluctuations. The parameters characterizing spin fluctuations in this system were estimated from NMR and magnetic measurements. The temperature dependence of susceptibility calculated from these parameters well reproduces the experimental results.     

Nuclear magnetic resonance relaxometry of the normal heart: Relationship between collagen content and relaxation times of the four chambers

The use of nuclear magnetic resonance (NMR) relaxation time measurements for characterization of abnormal cardiac tissue depends upon knowledge of variations of relaxation times of normal myocardium and determinants of these variations. We calculated in vitro NMR T₁ and T₂ relaxation times of canine myocardium from the four cardiac chambers, and determined hydroxyproline concentration (as a measure of collagen) and percent water content of the samples. We found both water content and T₁ relaxation time of the right ventricle to be significantly greater than the left atrium (p < 0.05). T₂ relaxation time of the left ventricle was found to be shorter than each of the other three chambers (p < 0.05). There were significant correlations between the spin-lattice relaxation time and both percent water content (r = 0.58) and hydroxyproline concentration (r = 0.45). A significant correlation was also found between T₂ relaxation time and hydroxyproline concentration (r = 0.49). When T₁ and T₂ were adjusted for water and hydroxyproline content, there was no longer any evidence for significant interchamber differences for either T₁ or T₂. These data suggest that differences in NMR relaxation times exist among the four chambers of the normal canine heart. Furthermore, a major determinant of myocardial spin-lattice relaxation time is tissue water content while both collagen content and percent water content significantly contribute to variability in cardiac chamber T₂ relaxation times.     

Molecular dynamics in solid pregnenolone studied by H spin–lattice relaxation

Spin–lattice relaxation times T₁ in solid pregnenolone have been studied over a wide range of temperatures, from 77 up to 417 K. The dynamic processes arising from C₃ motion of the three methyl substituents are separated, and their activation parameters are determined.     

NMR relaxation of protons in tissues and other macromolecular water solutions

Nuclear magnetic resonance (NMR) longitudinal (T₁) and transverse (T₂) relaxation parameters have been evaluated for protein solutions, cellular suspensions and tissues using both data from our laboratory and the extensive literature. It is found that this data can be generalized and explained in terms of three water phases: free water, hydration water, and crystalline water. The proposed model which we refer to as the FPD model differs from similar models in that it assumes that free and hydration water are two phases with distinct relaxation times but that T₁ = T₂ in each phase. In addition there is a single correlation time for each rather than a distribution as assumed in most other models. Longitudinal decay is predicted to be single exponent in character resulting from a fast exchange between the free and hydration compartments. Transverse decay is predicted to be multiphasic with crystalline (T₂ 10 μsec), hydration (T₂ 10 sec) and free (T₂ 100 sec) water normally visible. The observed or effective transverse relaxation times for both the hydration and free water phases are greatly affected by the crystalline phase and are much shorter than the inherent relaxation times.     

Validity of NMR pore-size analysis of cultural heritage ancient building materials containing magnetic impurities

NMR relaxation time distributions, obtained with laboratory and portable devices, are utilized to characterize the pore-size distributions of building materials coming from the Roman remains of the Greek-Roman Theatre of Taormina. To validate the interpretation of relaxation data in terms of pore-size distribution, comparison of results from standard and in situ NMR experiments with results of the mercury intrusion porosimetry (MIP) has been made. Although the pore-size distributions can be obtained by NMR in terms of either longitudinal (T₁) or transverse (T₂) relaxation times distributions, the shorter duration of the T₂ measurement makes it, in principle, preferable, although the determination of T₂ distributions is not necessarily an easy alternative to finding T₁ distributions. Among other things, the T₁ distribution is almost independent of the inhomogeneity of the magnetic field, while the T₂ distribution is strongly influenced by it. This paper was aimed at answering two questions: what are the validity limits to interpret NMR data in terms of pore-size distributions and whether the portable device can successfully be applied as a non-destructive and non-invasive tool for in situ NMR analysis of building materials, particularly those of Cultural Heritage interest.     

27Al NMR study in ZrNiAl

We have studied the microscopic properties of the hexagonal ZrNiAl, a model compound for a wide family of intermetallic compounds crystallizing in this type of structure, by using ²⁷Al NMR spectroscopy. We have investigated the lineshape of static and MAS NMR spectra as a function of magnetic field strength (4.7–9.4 T) and temperature (5–300 K). Our data indicate that the ²⁷Al NMR spectra result from a combined effect of quadrupole and anisotropic shift interactions. The ²⁷Al nuclei are in an environment characterized by the quadrupole coupling constant e²qQ/h of 3.3 MHz, asymmetry parameter η_Q of 0.42, isotropic shift δ_iso of 393 ppm, shift anisotropy δ_anis = δ_zz − (δ_xx + δ_yy)/2 of 150 ppm, and asymmetry factor η_S of 0.5. They are found to be temperature independent. The spin–lattice relaxation rate measured at 7.05 T is proportional to the temperature with T₁T = 135 s K. The mechanisms responsible for observed values of δ_iso, δ_anis, T₁T, and the enhanced Korringa constant are discussed.     

13C及29Si核磁共振研究苯乙烯-二甲基硅氧烷嵌段共聚物的弛豫及分子运动

用¹³C及²⁹Si核磁共振研究了苯乙烯(S)及二甲基硅氧烷(Si)嵌段共聚物中硅氧烷软段的固体及溶液谱的自旋-晶格弛豫时间T₁。固态嵌段共聚物主链²⁹Si及侧甲基¹³C的T₁都与均聚物的T₁相近,但在CdCl₃溶液中各种嵌段共聚物的T₁与均聚硅氧烷相差颇大。用偶极-偶极相互作用来解释高聚物的自旋-晶格弛豫。苯乙烯-二甲基硅氧烷嵌段共聚物具两相结构,所以嵌段共聚物中软段及硬段微区中链段的运动与在均聚物分子中链段的运动模式基本相同。而CdCl₃对聚苯乙烯或聚硅氧烷都是良溶剂,软段硬段之间有相互影响。所以其链段运动与均聚物不同,从而导致链段运动的相关时间τ_c变短和T₁的增长。     

Abnormal breakdown of Stokes–Einstein relation in liquid aluminium

We present the results of systematic molecular dynamics simulations of pure aluminium melt with a well-accepted embedded atom potential. The structure and dynamics were calculated over a wide temperature range, and the calculated results(including the pair correlation function, self-diffusion coefficient, and viscosity) agree well with the available experimental observations. The calculated data were used to examine the Stokes–Einstein relation(SER). The results indicate that the SER begins to break down at a temperature T_x(~1090 K) which is well above the equilibrium melting point(912.5 K).This high-temperature breakdown is confirmed by the evolution of dynamics heterogeneity, which is characterised by the non-Gaussian parameter α_2(t). The maximum value of α 2(t), α_(2,max), increases at an accelerating rate as the temperature falls below Tx. The development of α_(2,max) was found to be related to the liquid structure change evidenced by local fivefold symmetry. Accordingly, we suggest that this high-temperature breakdown of SER has a structural origin. The results of this study are expected to make researchers reconsider the applicability of SER and promote greater understanding of the relationship between dynamics and structure.     

Quantitative cerebral magnetic resonance imaging during ACTH treatment of multiple sclerosis

Serial MR scans were performed with the 2DFT imaging method and the filtered backprojection imaging method on 12 patients with multiple sclerosis in acute phase, 4 in a relapsing/remitting form, and 8 in a progressive form, before, during and after ACTH treatment. Both T₁ and T_2mono relaxation times, obtained by fitting transverse magnetization decay curves with a monoexponential function within the apparently normal white matter and the areas of increased signal, were measured. With the backprojection method it was possible to fit the transverse magnetization decay curve with a biexponential function and obtain T_2long and T_2short relaxation times. The T_2mono and T₁ relaxation times of the apparently normal white matter were significantly different from those obtained for volunteers, but no significant differences were found before, during, or after treatment. The transverse magnetization decay curves of the areas of increased signal were better fitted by a biexponential function. No significant changes in these relaxation times were observed after ACTH treatment. These results argue against an anti-oedematous action of ACTH and may suggest that it has an immunosuppressant effect.     

Selection of pulse sequences producing maximum tissue contrast in magnetic resonance imaging

The importance of spin density [N(H)] and spin-lattice (T₁) and spin-spin (T₂) relaxation in the characterization of tissue by nuclear magnetic resonance (NMR) is clearly recognized. This work considers which optimized pulse sequences provide the best tissue discrimination between a given pair of tissues. The effects of tissue spin density and machine-imposed minimum rephasing echo times (TE_MIN) for achieving maximum signal tissue contrast are discussed. A long TE_MIN sacrifices T₁-dependent contrast in saturation recovery (SR) and inversion recovery (IR) pulse sequences so that spin-echo (SE) becomes the optimum sequence to provide tissue contrast, due to T₂ relaxation. Pulse sequences providing superior performance may be selected based on spin density and T₁ and T₂ ratios for a given pair of tissues. Selection of the preferred pulse sequence and interpulse delay times to produce maximum tissue contrast is strongly dependent on knowledge of tissue spin densities as well as T₁ and T₂ characteristics. As the spin density ratio increases, IR replaces SR as the preferred sequence and SE replaces IR and SR as the pulse sequence providing superior contrast. To select the optimal pulse sequence and interpulse delay times, an accurate knowledge of tissue spin density, T₁ and T₂ must be known for each tissue.     

Temperature effects in directional elastic peak electron spectroscopy for the Cu(011) face: observation of the surface roughening transition

Polar profiles of directional elastic peak electron spectroscopy (DEPES) and directional Auger electron spectroscopy (DAES) were measured for the Cu(011) face in the vicinity of particular close-packed directions in the sample and for sample temperatures of 400<T<1200 K. For all directions investigated, the ln C versus T curve, where C is the contrast: C = 2(I_max−I_max)/(I_max + I_max) for a particular maximum in the polar profile, is composed of three linear parts. The slope of this particular part is different for the different maxima investigated but the breaks between the linear parts occur always at the temperatures T₁ ≈ 700 K and T₂ ≈ 1000 K. The former break is ascribed to the appearance of anharmonic thermal vibrations while the latter one indicates the surface roughening transition.

DEPES was applied for the first time in the investigation of the surface roughening transition and it was found to be a very convenient and effective method. The surface roughening temperature T_R ≈ 1000 K was found for the Cu(011) face, in an excellent agreement with theoretical predictions.