Anisotropy in Tendon Investigated in Vivo by a Portable NMR Scanner, the NMR-MOUSE

Ordered tissue like tendon is known to exhibit the magic-angle phenomenon in magnetic resonance investigations. Due to the anisotropic structure the transverse relaxation time T₂ depends on the orientation of the tendon in the magnetic field. In medical imaging, relaxation measurements of tendon orientation are restricted by the size of the object and the space available in the magnet. For humans, tendon orientation can only be varied within small limits. As a consequence, the magic-angle phenomenon may lead to a misjudgement of tendon condition. It is demonstrated that the NMR-MOUSE (mobile universal surface explorer), a hand-held NMR sensor, can be employed to investigate the anisotropy of T₂ in Achilles tendon in vivo. The NMR-MOUSE provides a convenient tool for analyzing the correlation of T₂ and the physical condition of tendon.     

The NMR-MOUSE: quality control of elastomers.

New applications of the NMR-MOUSE (mobile universal surface explorer) to non-destructive quality control of elastomers are reported. One example concern the thermal aging of fast clutches which was probed by measurements of 1H transverse relaxation time. Novel methodological developments show that 1H double-quantum filtered NMR signals can be generated in the inhomogeneous fields of the NMR-MOUSE for characterization of residual dipolar couplings. This technique was applied to characterize reference natural rubber samples with different crosslink density and carbon black and silica fillers.     

Anomalies of the natural convection of water near 3.98°C

Natural convection of water in a cylindrical cavity with an open surface at a temperature of about 3.98°C (temperature of the maximum water density) is accompanied by typical anomalies on time dependences of temperatures of water layers. In particular, stabilization of temperature T_st is observed in the bottom region of the cavity and duration of such stabilization t_st may reach several hours depending on the experimental conditions. The results for solutions of sodium chloride and ethanol at a relatively low rate of water cooling show that temperature T_st coincides with temperature T_max corresponding to the maximum density of solutions.     

The effects of burner stabilization on Fenimore NO formation in low-pressure, fuel-rich premixed CH4/O2/N2 flames

We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH₄/O₂/N₂ flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalence ratios between 1.3 and 1.5. The flame temperature is seen to decrease by 200-300 K, with a concomitant decrease in OH mole fraction, upon reducing the total flow rate from 5 to 3 L/min, thus increasing stabilization. At equivalence ratios between 1.3 and 1.5, this decrease in flow rate lowers the maximum CH mole fraction by a factor of 2, and the NO mole fraction by ∼40% in all flames studied. Integrating the reaction rate for CH + N₂ to estimate Fenimore NO formation, using the rate coefficient in GRI-Mech 3.0, and the measured temperatures and CH profiles show very good agreement with the measured NO mole fraction for ? = 1.3 and 1.4, supporting the current choice for this rate. This agreement also shows that the increase in residence time caused by increased stabilization is an important factor in the ultimate impact of the changes in CH mole fraction on NO formation. The results at ? = 1.5 suggest that substantial quantities of fixed nitrogen species, e.g., HCN, are only slowly oxidized in the post-flame zone under these conditions, leading to a significant discrepancy between the measured NO mole fraction and that obtained by integrating over the CH profile. Detailed calculations using GRI-Mech 3.0 predict the experimental results at ? = 1.3 nearly quantitatively, but show increasing differences with the measurements for both CH and NO profiles with increasing equivalence ratio.     

Influence of the redox state of QA on phycobilisome mobility in the cyanobacterium Synechocystis sp. strain PCC 6803

In a unicellular cyanobacterium, the mobile fraction of phycobilisome (PBS) was found to be maximum at a particular redox value of Q_A (i.e., 0.52). An upward or downward shift in the redox value leads to a decrease in this mobile fraction of PBS. Furthermore, the regulatory effect of the redox state of Q_A on PBS mobility was found to be independent of the effect exerted by the plastoquinone pool. These findings indicate for the first time that PBS mobility is regulated by the Q_A redox state in cyanobacteria. A possible working mechanism underlying this control is discussed.     

Temperature dependences of phonon and mobile-ion spectra in superionic conductor CuBr

The temperature dependence of far-infrared reflectivity spectra in sintered CuBr has been measured from 18 to 570 K. Phonon and mobile-ion parameters are evaluated by the fitting procedure with the factored form of the dispersion relation. A strong fourth order anharmonicity is assigned. Estimated values of optical dielectric constant and optical ionic mobility μ_op decrease with increasing temperature within a limited temperature region. For μ_op value, the effects of mobile ion scattering by optical phonons and of the expansion of interionic distance are discussed with respect to the phonon damping constant and the ionic character of the interionic force.     

Mixed alkali effect in boroarsenate glasses

We report, for the first time the study of mixed alkali effect (MAE) in boroarsenate glasses. Density, DSC, DC electrical conductivity and IR studies have been carried out for xK₂O-(40−x)Na₂O-50B₂O₃-10As₂O₃ glasses. The DC electrical conductivity was measured in the temperature range 100 °C to below the glass transition temperature. The strength of the MAE in T_g, DC electrical conductivity and activation energy has been determined. It is observed that the strength of MAE in DC electrical conductivity is less pronounced with increase in temperature. The results are explained by the structural model recently proposed by Swenson and coworkers, supporting molecular dynamic results. The IR studies show that the glass system contains BO₃ and BO₄ units in the disordered manner.     

AgTh2(PO4)3 — A new case of the non-hydrogen bonded phosphate ferroelectric

The basic crystallographic data of AgTh₂(PO₄)₃ single crystals have been determined for the first time by means of X-ray diffraction methods. The crystals are monoclinic, space group isCc with four formula units per unit cell. The dimensions of the unit cell are:a=17·385 Å,b=6·815 Å,c=8·148 Å,β=101·10°. Using the Sawyer and Tower method it has been proved that the crystals possess ferroelectric properties. Performing the measurements at room temperature the values of spontaneous polarization and coercive field in the direction normal to (100) face have been determined.     

Shaping the Sensitive Volume of a Single-Sided NMR-Sensor to Profile Cylindrical Samples with High Resolution

This work reports the construction of a single-sided magnet generating a sensitive volume with adjustable curvature. It is useful to profile cylindrical samples with high depth resolution. The sensor geometry is based on the Profile NMR-MOUSE, which generates a parabolic field profile with a quadratic coefficient that decreases with the distance from the magnet surface. Such field profiles approximate cylinder walls within limited angular range with negligible deviation. Then, by varying the working depth, shells of different diameter in the sample can be matched. Simulation and experiments conducted on phantoms confirm that a depth resolution of about 35 μm can be obtained. The sensor was used to profile the structure of a cylindric air spring bellows with high resolution. Besides resolving the fiber layers used to reinforce the rubber matrix, the ingress of hexane was detected via T ₂ changes of the material.     

Selective NMR excitation in strongly inhomogeneous magnetic fields

The NMR-MOUSE is a unilateral and mobile NMR sensor which operates with highly inhomogeneous magnetic fields. To produce a mobile NMR unit, RF excitation is sought, which can be produced with the most simple equipment, in particular nonlinear, low-power amplifiers, and to observe a free induction decay in strongly inhomogeneous fields, the excitation needs to be selective. The possibility to produce selective excitation by sequences of hard low-power radiofrequency pulses in the strongly inhomogeneous magnetic fields of the NMR-MOUSE is explored. The use of the DANTE sequence for selection of magnetization from parts of the sensitive volume was investigated for longitudinal and transverse magnetization by computer simulations and experiments. The spectra of the recorded FIDs and echo signals are in good agreement with those simulated for the excitation, which verifies the concept of the DANTE excitation. The results obtained are an important step towards a low-power operation of the NMR-MOUSE to improve its mobility.     

On the mechanism of diffusion in sodium beta alumina

A microscopic interstitialcy-type diffusion mechanism for sodium beta-alumina involving three crystallographically different types of cation sites but only two equilibrium configurations of interstitialcy pairs is proposed. The resulting cation-site occupation probabilities are shown to agree with the experimental neutron-diffraction data of Roth et al. For various sizes of the associated regions around the charge-compensating oxygen interstitials (in which Na⁺ ions are not freely mobile), the ratio of the radiotracer diffusivity with respect to the charge diffusivity (the so-called Haven ratio, H_R)is determined. In agreement with the measurements of Kim et al.,H_R is found to increase with increasing temperature as a result of the decrease in the average size of the associated regions. It is concluded that, while at lower temperatures all excess Na⁺ ions are found in the associated regions around the oxygen interstitials, with increasing temperature more and more of them are freely mobile in the unassociated regions of the conduction plane. The formation enthalpy associated with the thermally activated creation of mobile “interstitials” is determined to be about 0.05 eV. The slope of the slightly curved Arrhenius plot associated with the proposed mechanism therefore consists of the sum of the energy of formation of freely mobile interstitials and the energies of migration of two types of interstitialcy pairs. The Raman and IR-conductivity results are found to be compatible with this emerging picture for the microscopic diffusion process in sodium β-alumina. Spectroscopic diffusion techniques (NMR, internal friction, dielectric loss) show more than one apparent activation energy E^A while, in the same temperature region, the d.c. ionic conductivity yields a unique value of E^A; reasons for this discrepancy are discussed.     

Crystal field interpretation of 3-d metal substitution and superconductivity in YBa2Cu3O7

Experimental data on the superconducting critical temperature T_c of YBa₂(Cu_1−xM_x)₃O_7−y, where M is a 3D transition ion are reviewed and shown to correlate closely with the difference in crystal field stabilization energies for Cu2 sites in the 2D planes and Cu1 sites in the 1D chains respectively. Thus superconductivity is depressed when the 1D chain is modified.     

Degradation of historical paper: nondestructive analysis by the NMR-MOUSE

The NMR-MOUSE is a mobile sensor for single-sided NMR inspection of organic materials which takes advantage of the principles of magnetic resonance and inside-out-NMR. Historical books dating from the 17th century were measured at different points by positioning the NMR-MOUSE on the paper. Different degrees of paper degradation can be discriminated from the regularized inverse Laplace transform of the envelope of the acquired echo signals. For the first time the degradation of historical paper was characterized entirely nondestructively by NMR. As a contribution to current preservation efforts, NMR shows great promise for future use in damage assessment of historical documents.     

Mixed ionic conduction in solid KHF2

From EMF measurements it can be concluded that there is no significant electronic conductivity in KHF₂. In the relatively good conducting high temperature β-phase the following transport numbers are found: t_K≈0,25 and t_F≈0,75 while t_H≈0 as was concluded from changes in chemical composition on electrolysis in Hittorf-Tubandt type experiments. From current-time characteristics it follows that in the low-conducting low temperature α-phase, the proton is the only mobile charge carrier in this phase, i.e. t_H≈1. It also proved that the d.c. conductivity of single crystals measured with hydrogen permeable electrodes coincides with the zero-frequency conductivity found by extrapolation of a.c. data.     

Anomalous diffusion of hydrogen in β-VHx: Pulsed-NMR experiments on H1

Diffusion of hydrogen atoms in β-VH_x has been studied by means of a pulsed-NMR technique. A large temperature dependence of the activation energy towards the phase transition temperature βα has been noted, and is interpreted in terms of a saddle point energy and the energy of stabilization of c-octahedral sites relative to other sites.     

The nature of domain stabilization in ferroelectric perovskites

Ferroelectric perovskites, such as Pb(Ti,Zr)O₃ and BaTiO₃, are subject to ageing effects, caused by a gradual stabilization of the ferroelectric domain structure. We studied the development of this stabilization in Mn-doped BaTiO₃ monocrystals having a special kind of domain structure. We concluded from measurements of the growth of the internal bias field E_i and the change of the sideways 180° domain-wall mobility with time, that the fairly strong stabilization in this material originates from volume effects, which implies a gradual reorientation of polar defects with respect to the direction of the spontaneous polarization, both 180° domain-wall pinning and surface-layer effects being completely absent. A proposal is made about the nature of these defects.     

Dynamic modeling of cyclotetracubyl thermal decomposition

Cyclotetracubyl (C₈H₆)₄ is the smallest possible two-dimensional oligomer constructed from cubylene units. An original quantum-chemical method for molecular modeling is for the first time used to determine its thermokinetic parameters (activation energy and frequency factor). The temperature dependence of the lifetime of cyclotetracubyl over the temperature range 700–1600 K is examined. The results are compared with the data for individual cubane and linear tetracubyl in order to analyze the influence of the dimension of oligomers on their thermal stability and decomposition mechanisms. Modeling of heavier oligomers, C₇₂H₄₈, C₁₂₈H₈₀, and C₂₀₀H₁₂₀, made it possible to obtain, by extrapolation, the binding energy per cubylene fragment in an infinite two-dimensional layer (E _b = 8.62 eV/mer) and to determine the dependence of the HOMO-LUMO gap on the characteristic size of the oligomer.     

Negative magnetoresistance and nonlinear conduction in Ti0.99V0.01Se2

Both magnetic and electric field dependences of transport coefficients are investigated on the layered material Ti_1-xV_xSe₂ (x = 0.01). In contrast to semimetallic TiSe₂, the resistivity of the V-doped samples increases with decrease of temperature even in the low temperature region. At liquid helium temperatures it is found that the resistivity is strongly dependent on electric field strength. The behaviour of the nonlinear conduction is similar to that observed in 1T-TaS₂. In the low field (Ohmic) region anomalously large negative mangetoresistance is observed, Δ?/?₀ = -80% at 1.6 K and 60 KOe. Moreover the Hall coefficient is also found to depend on both magnetic and electric fields. All the experimental data suggests that mobile carriers are excited by the applied fields.     

Spin relaxation studies on conducting poly(tetrathiafulvalene)

Magnetic parameters and the relaxation behavior of paramagnetic centers in an iodine-doped poly(tetrathiafulvalene) semiconductor with a d.c. conductivity of 10^?5 S·cm^?1 have been studied using mainly the 2 mm waveband EPR technique in the temperature range of 110–270 K. The EPR line shape analysis confirms the existence of immobile radicals pinne on short polymer chains and mobile polarons with different relaxation parameters in slightly doped poly(tetrathiafulvalene). The temperature dependences of electron spin-lattice and spin-spin relaxation times of paramagnetic centers of both types have been determined independently using the saturation method at the operation frequency ν _e = 140 GHz. An anisotropic slow libration of immobile polarons with an activation energy of 0.02 eV have been registered for the first time using the saturation transfer EPR method. The temperature dependences of intrachain diffusion and interchain hopping rates in poly(tetrathiafulvalene) are determined from theT ₁ andT ₂ EPR data. The interchain spin dynamics is shown to correlate with libration of polarons trapped on polymer chains and is in good agreement with a hopping charge transport mechanism.     

Effect of the deviation from stoichiometry on cation self-diffusion and isotope effect in wüstite,Fe1−xO

Diffusion of ⁵⁹Fe in Fe_1xO crystals has been measured by a serial-sectioning technique as a function of temperature and deviation from stoichiometry. The results indicate that the diffusivity increases slightly at 1200°C, decreases at 802°C with an increase in x, and is insensitive to change in x at 1003°C. The temperature dependence of the cation diffusivity in Fe_0.94O is given by the expression, $\text{D=(0.6±0.5)×10}{}^{\mathrm{?3}}\text{exp(?29350 ±}\text{300}\text{RT}\text{)cm}{}^2\text{/se}$ the temperature range 700–1340°C. The isotope effect for cation self-diffusion was measured by simultaneous diffusion of ⁵²Fe and ⁵⁹Fe in Fe_1?xO at various temperatures and values of x. Although the measured values of fΔK are independent of temperature within the limits of experimental error, they decrease with an increase in the deviation from stoichiometry. The experimental results appeared to be consistent with the diffusion of Fe ions via “free mobile vacancies” that coexist with defect clusters. As a consequence of a “site-blocking” effect, the mobility of “free mobile vacancies” and the apparent correlation factor for cation tracer diffusion decrease with an increase in deviation from stoichiometry.