Effects of L-spin longitudinal quadrupolar relaxation in heteronuclear recoupling and S-spin magic-angle spinning NMR

In experiments on S–L heteronuclear spin systems with evolution of the S-spin magnetization under the influence of a quadrupolar nucleus (L-spin), effects of longitudinal quadrupolar (T_1Q) relaxation of the L-spin coherence on the sub-millisecond time scale have been documented and explored, and methods for minimizing their effect have been demonstrated. The longitudinal relaxation results in heteronuclear dephasing even in the reference signal S₀ of S{L} REDOR, REAPDOR, RIDER, or SPIDER experiments, due to T_1Q-relaxation of the transiently generated S_yL_z coherence, reducing or even eliminating the observable dephasing ΔS. Pulse sequences for measuring an improved reference signal S₀₀ with minimal heteronuclear recoupling but the same number of pulses as for S₀ and S have been demonstrated. From the observed intensity ΔS₀ = S₀₀ − S₀ and the SPIDER signal ΔS/S₀, T_1Q can be estimated. Accelerated decays analogous to the dipolar S₀ curves will occur in T₂ measurements for J-coupled S–L spin pairs. Even in the absence of recoupling pulses, fast T_1Q relaxation of the unobserved nucleus shortens the transverse relaxation time T_2S,MAS of the observed nucleus, in particular at low spinning frequencies, due to unavoidable heteronuclear dipolar evolution during a rotation period. The observed spinning-frequency dependence of T_2S,MAS matches the theoretical prediction and may be used to estimate T_1Q. The effects are demonstrated on several ¹³C{¹⁴N} spin systems, including an arginine derivative, the natural N-acetylated polysaccharide chitin, and a model peptide, (POG)₁₀.     

Time Correlations in Fluid Transport Obtained by Sequential Rephasing Gradient Pulses

We present a basic experiment by which the evolution of the displacement probability density (propagator) of static or flowing fluid inNsuccessive time intervals is obtained by single labeling, coupled with multiple rephasing events during the course of a pulsed field-gradient sequence. We term this type of sequence SERPENT: SEquential Rephasing by Pulsed field-gradients Encoding N Time-intervals. Realizations of the SERPENT experiment for the caseN= 2 which include spin echo, stimulated echo, and Carr–Purcell pulse sequences are suggested. They have in common a spatial spin-labeling of the initial magnetization by a gradient of area q₀, followed by successive rephasing via gradients q₁and q₂at timest= Δ₁andt= Δ₂, respectively, where q₀+ q₁+ q₂= 0. A two-dimensional Fourier transform with respect to q₁and q₂gives directly the joint probability densityW₂(R₁, Δ₁; R₂, Δ₂) for displacements R₁and R₂in times Δ₁and Δ₂, respectively. q₁and q₂may be in arbitrary directions. Assuming R₁R₂, the correlation coefficient ρ_R1,R2then reflects the time-history of the fluctuating velocities. The behavior of the cross moment R₁(Δ₁) · R₂(Δ₂) can be obtained from either a full two-dimensional or a set of one-dimensional SERPENT measurements. Experimental results are presented for water flowing through a bed of packed glass beads. While Δ₁is appropriately chosen to sample the short-time velocity field within the system, increasing Δ₂clearly shows the loss of correlation when the average fluid element displacement exceeds the bead diameter.     

Brownian Motion with Dry Friction

A small object (Solid or droplet) is placed on a horizontally vibrating plate, imposing an acceleration γ(t) in the form of a white noise. The object experiences dry friction (due to soild/solid interaction, or to contact angle hysteresis in the case of a droplet). The object is driven by a force γ(t) – Δσ(t) where σ(t), =±1, depending on the sign of the velocity. We discuss the motion at two levels: (i) in terms of simple scaling laws, (ii) by a propagator technique. (a) When Δ is below a certain crossover value Δ*, we expect an unperturbed (Langevin) Brownian motion. (b) When Δ > Δ*, we expect a reduced diffusion coefficient proportional to Δ⁻⁴ for small Δ.     

Interaction of oxovanadium(IV) with carboxylic ligands in aqueous solution: A thermodynamic and visible spectrophotometric study

The hydrolysis of VO²⁺ and the complex with sulfate were studied potentiometrically, spectrophotometrically and calorimetrically, in NaCl aqueous solution (0 < I ≤ 1 mol L^− 1) and at t = 25 °C. The formation of two hydrolytic species VO(OH)⁺ and VO₂(OH)₂²⁺ and one complex with sulfate was found, with log β = − 5.65 for the reaction VO²⁺ + H₂O = VO(OH)⁺ + H⁺, log β = − 7.02 for the reaction 2VO²⁺ + 2H₂O = (VO)₂(OH)₂²⁺ + 2H⁺ and log K = 1.73 for VOSO₄⁰ species (at I = 0.1 mol L^− 1 and t = 25 °C). For these species, using calorimetric data, ΔH and TΔS values were also obtained. By using the above values, interactions of VO²⁺ with acetate (ac), malonate (mal), succinate (suc), 1,2,3-propanetricarboxylate (tca) and 1,2,3,4-butanetetracarboxylate (btc) ligands were studied potentiometrically and spectrophotometrically. The formation of ML⁺, ML₂⁰ and MLOH⁰ for ac; ML⁰, MLH⁺, ML₂²⁻ and ML₂H⁻ for mal; ML⁰, MLH⁺ and MLOH⁻ for suc; ML⁻ and MLH⁰ for tca and ML²⁻, MLH⁻ and MLH₂⁰ for btc were found. Formation constants are reported at I = 0.1 mol L^− 1, together with SIT parameters for the dependence on ionic strength. By visible spectrophotometric measurements, λ_max and ε_max values for the relevant species in solution were determined.     

Study of nuclear quadrupole interactions and quadrupole Raman processes of Ga and Ga in a β-Ga2O3:Cr single crystal

Nuclear magnetic resonance (NMR) data and the spin–lattice relaxation times, T₁, of ⁶⁹Ga and ⁷¹Ga nuclei in a β-Ga₂O₃:Cr³⁺ single crystal were obtained using FT NMR spectrometry. Four sets of NMR spectra for ⁶⁹Ga (I = 3/2) and ⁷¹Ga (I = 3/2) were obtained in the crystallographic planes. The ⁶⁹Ga and ⁷¹Ga nuclei each had two chemically inequivalent Ga_I and Ga_II centers. Each of the ⁶⁹Ga and ⁷¹Ga isotopes yielded two different central NMR resonance lines originating from Ga_I and Ga_II sites. The nuclear quadrupole coupling constants and asymmetry parameters of ⁶⁹Ga_I, ⁶⁹Ga_II, ⁷¹Ga_I, and ⁷¹Ga_II centers in a β-Ga₂O₃:Cr³⁺ crystal were obtained. Analysis of the EFG tensor principal axes (PAs) for Ga nuclei and the ZFS tensor PAs for the Cr³⁺ ion confirmed that the Cr³⁺ paramagnetic impurity ion substitutes for the Ga³⁺ ion in the oxygen octahedron. In addition, the temperature dependencies of the ⁶⁹Ga and ⁷¹Ga relaxation rates were consistent with Raman processes, as T₁⁻¹ ∝ T². Even though the Cr³⁺ impurities are paramagnetic, the relaxations were dominated by electric quadrupole interactions of the nuclear spins in the temperature range investigated.     

Fermi-liquid instability at magnetic–nonmagnetic quantum phase transitions

In metals with strong electronic correlations such as heavy-fermion systems or itinerant-electron magnets it is possible to change from a magnetically ordered to a nonmagnetic groundstate by variation of an external parameter such as composition or pressure. In principle a transition between these groundstates can occur at zero temperature. In case of a continuous transition quantum fluctuations take the role of thermal fluctuations in finite-temperature transitions. The abundance of low-lying magnetic excitations leads in the vicinity of the quantum critical point to unusual behavior of thermodynamic and transport properties at low temperatures T not envisioned by the classical Fermi-liquid behavior that is observed even in strongly correlated electron systems away from the quantum phase transition. We discuss in detail a few examples of this ‘non-Fermi-liquid behavior', viz., CeCu_6−xAu_x, Ce_1−xLa_xRu₂Si₂, Ce₇Ni₃, CeCu₂Si₂ and CeCu₂Ge₂, CePd₂Si₂, and UCu_1−xPd_x. In CeCu_6−xAu_x the very unusual low-T behavior of the linear specific-heat coefficient C/T−ln(T/T₀) and of the resistivity ΔρT can be attributed to quasi-two-dimensional fluctuations as determined from inelastic neutron scattering. The systems CeCu₂Ge₂ and CePd₂Si₂ are particuarly interesting since here the magnetic order which is suppressed under hydrostatic pressure gives way to superconductivity, suggesting that spin fluctuations mediate the formation of Cooper pairs at least in the latter system.     

Millimeter-wave spectrum of DCCCHO in the ground vibrational state

About 140 a- and b-type millimeter-wave transitions of propynal-d₁, DCCCHO, were measured in the ground vibrational state. The accurate rotational and centrifugal distortion constants were determined from the observed frequencies including the previous microwave measurements. Seven microwave transitions observed by infrared-microwave double resonance were also included in the analysis. The determined constants are A = 66778.016(12), B = 4463.8489(7), C = 4177.7950(7), Δ_J = 0.0015919(5), Δ_JK = −0.139214(13), Δ_K = 9.4328(18), δ_J = 0.0002885(4), δ_K = 0.03069(4), H_JK = −0.817(13) × 10⁻⁶, H_KJ = −9.62(4) × 10⁻⁶, H_K = 0.00255(8), h_J = 0.0047(3) × 10⁻⁶, in MHz.     

Thermodynamic conditions for formation of single phase in Bi-superconductor thin films

High quality BSCCO thin films have been fabricated by means of an ion beam sputtering at various substrate temperatures, T_sub, and ozone gas pressures, pO₃. The correlation diagrams of the BSCCO phases appearing against T_sub and pO₃ have been established in the 2212 and 2223 compositional films. In spite of 2212 compositional sputtering, Bi2201 and Bi2223 phases as well as Bi2212 have emerged as stable phases depending on T_sub and pO₃. From these results, the thermodynamic evaluations of ΔH and ΔS, which are related with Gibbs’ free energy change for single Bi2212 or Bi2223 phase have been performed.     

Study of the interaction of Na9[SbW9O33]·19.5H2O with bovine serum albumin: Spectroscopic and voltammetric methods

The interaction of Na₉[SbW₉O₃₃]·19.5H₂O (SbW) with bovine serum albumin (BSA) is studied by spectroscopic and voltammetric methods. Absorption spectroscopy of BSA and the linear sweep voltammetry of SbW proved the formation of ground-state SbW–BSA complex. Fluorescence quenching of serum albumin by SbW is also found to be a static quenching process. The binding constant K_a is 4.13×10⁴ L mol⁻¹ for SbW–BSA at pH 7.40 Tris–HCl buffer at 295 K. The number of binding sites and the apparent binding constants at different temperatures are obtained from the analysis of the fluorescence quenching data. The thermodynamic parameters determined by the Van’t Hoff analysis of the binding constants (ΔH=−80.01 kJ mol⁻¹ and ΔS=−182.85 J mol⁻¹ K⁻¹) clearly show that the binding is absolutely entropy driven. Hydrogen bonding and van der Waals interaction force play major role in stabilizing the complex. The effect of SbW on the conformation of BSA is analyzed using synchronous fluorescence spectroscopy.     

Conductometric and thermodynamic studies on the ionic association of HCOONH4, phCOONH4, HCOONa and phCOONa in aqueous–organic solvents

The specific conductance of ammonium formate, ammonium benzoate, sodium formate and sodium benzoate in (10%, 20% and 30% (W/W)) methanol–water, ethanol–water and glycerol–water mixtures at different temperatures (293, 298, 303 and 308 K) was measured.The molar conductance (Λ), limiting molar conductance (Λ₀), limiting ionic conductance (λ₀), association constants (K_A), the activation energy of the transport process (E_a), Walden product (Λ₀η₀), hydrodynamic radii (1/r_s⁺ + 1/r_s⁻)^− 1, transfer numbers of the studied ions (t), standard thermodynamic parameters of association (ΔG_A, ΔH_A and ΔS_A) were calculated and discussed.The results show that, the molar conductance and the limiting molar conductance values were decreased as the relative permittivity of the solvent decreased while, the association constant increased. Also the results show that the molar conductance, the limiting molar conductance and the association constant values were increased as the temperature increased indicating that the association process is an endothermic one.     

Electron heating in a submicron-size n GaAs wire

We have studied electron heating in a submicron-size GaAs wire from 4.2 K to 50 K. We find that the energy relaxation rate for the electrons is of the form τ_E⁻¹ = α + βT_eⁿ where α, β are constants and T_e is the electron temperature. We associate the temperature-independent term with a quasi-elastic surface scattering process in which an electron losses 1% of its energy at each collision. The temperature dependent term may be due to electron-phonon scattering. It is possible to fit the data to 2 < n < 3.     

Internal dynamics of hydroxymethyl rotation from CH2 cross-correlated dipolar relaxation in methyl-β- -glucopyranoside

Conventional relaxation parameters (T₁⁻¹, T₂⁻¹, and NOE), obtained at different temperatures and magnetic fields, are reported for the hydroxymethyl (C6) carbon in methyl-β- -glucopyranoside in a D₂O/DMSO cryosolvent. These data are interpreted with the Lipari–Szabo model. In addition, two-field measurements of longitudinal and spin-locked relaxation rates related to the cross-correlated carbon–proton dipole–dipole interactions for the same carbon are reported. The complete data set consisting the conventional and cross-correlated relaxation parameters is interpreted using a new “hybrid” approach, in which the Lipari–Szabo model for the auto-correlated spectral densities is combined with the two-site jump model for the cross-correlated spectral densities, with the global correlation time as a common parameter. The two-site jump rates thus obtained are in reasonable agreement with the ultrasonic relaxation measurements, and have reasonable temperature dependence.     

Multi-components of T2 relaxation in ex vivo cartilage and tendon

The multi-components of T₂ relaxation in cartilage and tendon were investigated by microscopic MRI (μMRI) at 13 and 26 μm transverse resolutions. Two imaging protocols were used to quantify T₂ relaxation in the specimens, a 5-point sampling and a 60-point sampling. Both multi-exponential and non-negative-least-square (NNLS) fitting methods were used to analyze the μMRI signal. When the imaging voxel size was 6.76 × 10⁻⁴ mm³ and within the limit of practical signal-to-noise ratio (SNR) in microscopic imaging experiments, we found that (1) canine tendon has multiple T₂ components; (2) bovine nasal cartilage has a single T₂ component; and (3) canine articular cartilage has a single T₂ component. The T₂ profiles from both 5-point and 60-point methods were found to be consistent in articular cartilage. In addition, the depletion of the glycosaminoglycan component in cartilage by the trypsin digestion method was found to result in a 9.81–20.52% increase in T₂ relaxation in articular cartilage, depending upon the angle at which the tissue specimen was oriented in the magnetic field.     

IR absorption spectrum (4200–3100 cm) of H2O and (H2O)2 in CCl4. Estimates of the equilibrium constant and evidence that the atmospheric water absorption continuum is due to the water dimer

IR absorption spectra, 4200–3100 cm⁻¹, of water in CCl₄ solutions are presented. It is shown that for saturated solutions significant amounts of water are present as dimer (ca. 2%). The IR spectra of the monomer and dimer are retrieved. The integrated absorption coefficients of the monomer absorption are significantly enhanced relative to the gas phase values. The dimer spectrum consists of 5 bands, of which 4 were expected from data from cold beams and cold matrices. The origin of the “extra” band is discussed. In addition it is argued that the dimer absorption bands intensities must be enhanced relative to the gas phase values. Based on recent calculations of band strengths, and observed frequency shifts relative to the gas phase, the intensity enhancement factors are estimated as well as the monomer/dimer equilibrium constant in CCl₄ solution at T=296 K (K_c=1.29 mol⁻¹ L). It is noted that the observed dimer spectrum has a striking resemblance with the water vapour continuum determined by Burch in 1985 which was recently remeasured by Paynter et al. and it is concluded that the atmospheric water absorption continuum in the investigated spectral region must be due to water dimer. Based on the newly published spectral data a revised value of the gas phase equilibrium constant is suggested (K_p=0.035 atm⁻¹ at T=296 K) as well as a value for the standard enthalpy of formation, ΔH⁰=15.4 kJ mol⁻¹.     

Spectral characterization and energy levels of Cr:Sc2(MoO4)3 crystal

This paper reports the spectral properties and energy levels of Cr³⁺:Sc₂(MoO₄)₃ crystal. The crystal field strength Dq, Racah parameter B and C were calculated to be 1408 cm⁻¹, 608 cm⁻¹ and 3054 cm⁻¹, respectively. The absorption cross sections σ_α of ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ transitions were 3.74×10⁻¹⁹ cm² at 499 nm and 3.21×10⁻¹⁹ cm² at 710 nm, respectively. The emission cross section σ_e was 375×10⁻²⁰ cm² at 880 nm. Cr³⁺:Sc₂(MoO₄)₃ crystal has a broad emission band with a broad FWHM of 176 nm (2179 cm⁻¹). Therefore, Cr³⁺:Sc₂(MoO₄)₃ crystal may be regarded as a potential tunable laser gain medium.     

Changes in Porcine Muscle Water Characteristics during Growth—An in Vitro Low-Field NMR Relaxation Study

This study investigates the effects of developmental stage and muscle type on the mobility and distribution of water within skeletal muscles, using low-field ¹H-NMR transverse relaxation measurements in vitro on four different porcine muscles (M. longissimus dorsi, M. semitendinosus, M. biceps femoris, M. vastus intermedius) from a total of 48 pigs slaughtered at various weight classes between 25 kg and 150 kg. Principal component analysis (PCA) revealed effects of both slaughter weight and muscle type on the transverse relaxation decay. Independent of developmental stage and muscle type, distributed exponential analysis of the NMR T₂ relaxation data imparted the existence of three distinct water populations, T_2b, T₂₁, and T₂₂, with relaxation times of approximately 1–10, 45–120, and 200–500 ms, respectively. The most profound change during muscle growth was a shift toward faster relaxation in the intermediate time constant, T₂₁. It decreased by approx. 24% in all four muscle types during the period from 25 to 150 kg live weight. Determination of dry matter, fat, and protein content in the muscles showed that the changes in relaxation time of the intermediate time constant, T₂₁, during growth should be ascribed mainly to a change in protein content, as the protein content explained 77% of the variation in the T₂₁ time constant. Partial least squares (PLS) regression revealed validated correlations in the region of 0.58 to 0.77 between NMR transverse relaxation data and muscle development for all the four muscle types, which indicates that NMR relaxation measurements may be used in the prediction of muscle developmental stage.     

Influence of hydrogenation on the electronic structure and the itinerant-electron metamagnetic transition in strong magnetocaloric compound La(Fe0.88Si0.12)13

The influence of interstitial hydrogen on the electronic structure and the itinerant-electron metamagnetic (IEM) transition in strong magnetocaloric compound La(Fe_0.88Si_0.12)₁₃H_1.6 has been investigated by Mössbauer spectroscopy. A slight change in the average hyperfine field at 4.2 K was observed after hydrogen absorption. In contrast, the thermally induced first-order transition related to the IEM transition for y=1.6 appears at the Curie temperature T_C=330 K, much higher than T_C=195 K for y=0.0. The increase of isomer shift δ_IS at 4.2 K indicates that the valence electron transfer from hydrogen to Fe is negligibly small, hence the change in the magnetic state is closely associated with a volume expansion after hydrogen absorption. No change in shape by hydrogenation for the Mössbauer spectra in the paramagnetic state has been observed except for a difference in only δ_IS, indicating the volume expansion by hydrogenation is isotropic. Accordingly, the significant increase of T_C by hydrogen absorption is attributed to the magnetovolume effect associated with characteristic feature in IEM compounds. A discontinuous change of ferromagnetic moment, ΔM, around T_C has been observed by Mössbauer spectra, as expected from the magnetization measurement. The value of ΔM is slightly decreased by increase of T_C after hydrogenation but its magnitude is almost the same due to the stabilization of ferromagnetic moment. As a result, strong magnetocaloric effect is maintained up to room temperature after hydrogenation.     

Numerical renormalization group studies of SU(4) Kondo effect in quantum dots

We theoretically study an enhancement of the Kondo effect in quantum dots with two orbitals and spin . The Kondo temperature and conductance are evaluated as functions of energy difference Δ between the orbitals, using the numerical renormalization group method. The Kondo temperature is maximal around the degeneracy point (Δ=0) and decreases with increasing |Δ| following a power law, T_K(Δ)=T_K(0)(T_K(0)/|Δ|)^γ, which is consistent with the scaling analysis. The conductance at T=0 is almost constant 2e²/h. Both the orbitals contribute to the conductance around Δ=0, whereas the current through the upper orbital is negligibly small when |Δ|T_K(0). These are characteristics of SU(4) Kondo effect.     

Study on the interaction between theasinesin and human serum albumin by fluorescence spectroscopy

The binding properties on theasinesin to human serum albumin (HSA) have been studied for the first time using fluorescence spectroscopy in combination with UV–vis absorbance spectroscopy. The results showed that theasinesin strongly quenched the intrinsic fluorescence of HSA through a static quenching procedure, and non-radiation energy transfer happened within molecules. The number of binding site was 1, and the efficiency of Förster energy transfer provided a distance of 4.64 nm between tryptophan and theasinesin binding site. At 298, 310 and 323 K, the quenching constants of HSA–theasinesin system were 2.55×10³, 2.16×10³ and 1.75×10³ mol L⁻¹. ΔH^θ, ΔS^θ and ΔG^θ were obtained based on the quenching constants and thermodynamic theory (ΔH^θ<0, ΔS^θ>0 and ΔG^θ<0). These results indicated that hydrophobic and electrostatic interactions are the mainly binding forces in the theasinesin–HSA system. In addition, the results obtained from synchronous fluorescence spectra showed that the binding of theasinesin with HSA could induce conformational changes in HSA.     

The influence of indium on the structural modification of the amorphous Ge–In–Se system

The effect of both the chemical composition and the nature of the chemical bonding of amorphous alloyed samples of Ge_xIn_ySe_100−x−y prepared under vacuum with x=20, 4y15 on the efficiency of the structural modification Δφ is analysed using a simple consideration based on the coordination number Z, and the number of topological constraints N_co. The previously obtained parameters have been used for the determination of the number of continuous deformation (i.e. zero-frequency modes f ), and for the estimation of the cohesive energies of these glasses, assuming simple additivity of bond energies. A trial has been made to correlate the results of this paper with the previously published data of glass transition temperature T_g, activation energy ₀ and the shift of the K-absorption edge (ΔE_K) of the composition of vacuum prepared Ge_xIn_ySe_100−x−y. It was found that there is a correlation between the lone-pair electrons and the stability of the vitreous state. According to the criterion of Liang, the above correlation has been interpreted in terms of Δφ.