o-Semiquinonato and o-iminosemiquinonato rhodium complexes. EPR study of the reactions in coordination sphere of rhodium

Chemical exchange saturation transfer (CEST) processes in aqueous systems are quantified by evaluation of z-spectra, which are obtained by acquisition of the water proton signal after selective RF presaturation at different frequencies. When saturation experiments are performed in vivo, three effects are contributing: CEST, direct water saturation (spillover), and magnetization transfer (MT) mediated by protons bound to macromolecules and bulk water molecules. To analyze the combined saturation a new analytical model is introduced which is based on the weak-saturation-pulse (WSP) approximation. The model combines three single WSP approaches to a general model function. Simulations demonstrated the benefits and constraints of the model, in particular the capability of the model to reproduce the ideal proton transfer rate (PTR) and the conventional MT rate for moderate spillover effects (up to 50% direct saturation at CEST-resonant irradiation). The method offers access to PTR from z-spectra data without further knowledge of the system, but requires precise measurements with dense saturation frequency sampling of z-spectra. PTR is related to physical parameters such as concentration, transfer rates and thereby pH or temperature of tissue, using either exogenous contrast agents (PARACEST, DIACEST) or endogenous agents such as amide protons and -OH protons of small metabolites.     

Synthesis of spin labelled silica and EPR molecular dynamics study at silica–polymer interfaces

Information concerning the interface structure in filler/polymer composites is of key importance for the rationalization of reaction mechanisms in mechano‐chemical (extrusion, blending, etc.), thermal or radiation induced free radical processes and for elucidating the factors underlying the reinforcing mechanism. The analysis of the chain dynamics is a suitable tool for undertaking such investigations because any reactivity parameter (rate constants, collisional frequencies, activation energies) and bonding interactions are strictly related to the mobility of the interacting centres. EPR spectroscopy coupled with specific spin labelling at the filler/polymer interface is a tool for making such novel perspective available. In this work, a spin labelling study of the molecular motion at the filler–rubber interface in a silica–SBR blend is reported. Spin labels of different length, spanning a 9–11 Å depth and linked to the surface of silica particles, were prepared and used for determining the rotational diffusion tensors, the T₅₀ and order parameter in silica/SBR interfaces. The measurements carried out as a function of the temperature in comparison with unbound spin probes dispersed in the rubber matrix have afforded information consistent with the structure of the interfaces predicted by molecular–level theoretical models. Copyright © 2010 John Wiley & Sons, Ltd.     

NMR dipolar constants of motion in liquid crystals: Jeener–Broekaert, double quantum coherence experiments and numerical calculation on a 10-spin cluster

Two proton quasi-equilibrium states were previously observed in nematic liquid crystals, namely the and quasi-invariants. Even though the experimental evidence suggested that they originate in a partition of the spin dipolar energy into a strong and a weak part, respectively, from a theoretical viewpoint, the existence of an appropriate energy scale which allows such energy separation remains to be confirmed and a representation of the quasi-invariants is still to be given. We compare the dipolar NMR signals yielded both by the Jeener–Broekaert (JB) experiment as a function of the preparation time and the free evolution of the double quantum coherence (DQC) spectra excited from the state, with numerical calculations carried out from first principles under different models for the dipolar quasi-invariants, in a 10-spin cluster which represents the 5CB (4^′-pentyl-4-biphenyl-carbonitrile) molecule. The calculated signals qualitatively agree with the experiments and the DQC spectra as a function of the single-quantum detection time are sensible enough to the different models to allow both to probe the physical nature of the initial dipolar-ordered state and to assign a subset of dipolar interactions to each constant of motion, which are compatible with the experiments. As a criterion for selecting a suitable quasi-equilibrium model of the 5CB molecule, we impose on the time evolution operator consistency with the occurrence of two dipolar quasi-invariants, that is, the calculated spectra must be unaffected by truncation of non-secular terms of the weaker dipolar energy. We find that defining the quasi-invariant as the subset of the dipolar interactions of each proton with its two nearest neighbours yields a realistic characterization of the dipolar constants of motion in 5CB. We conclude that the proton-spin system of the 5CB molecule admits a partition of the dipolar energy into a bilinear strong and a multiple-spin weak contributions therefore providing two orthogonal constants of motion, which can be prepared and observed by means of the JB experiment. This feature, which implies the existence of two timescales of very different nature in the proton-spin dynamics, is ultimately dictated by the topology of the spin distribution in the dipole network and can be expected in other liquid crystals. Knowledge of the nature of the dipolar quasi-invariants will be useful in studies of dipolar-order relaxation, decoherence and multiple quantum NMR experiments where the initial state is a dipolar-ordered one.     

Theoretical study of the dependence of EPR spectra on local structure for octahedral Cr3+ centres in oxides and fluorides series

A theoretical method for investigating the inter-relation between the EPR parameters and local structure has been established on the basis of the complete energy matrices for 3d³ configuration ions in both the trigonal and tetragonal ligand fields. By means of this method, the local structure of the octahedral Cr³⁺ centres in double molybdates series and spinels series as well as the perovskite-type fluorides series has been studied systematically. Furthermore, the dependence of the EPR zero-field splitting parameter D on the local structure parameters in both trigonal and tetragonal ligand-fields has been revealed, simultaneously. The inter-relation between the EPR parameters D and Δg(g _// ??g _⊥) is also elucidated.     

Neutron spectroscopy study of magnons in the austenite and martensite phases of a Ni-Mn-Ga Heusler alloy

The low energy region of magnon excitations of an off-stoichiometric Ni_49.1Mn_29.4Ga_21.5 single crystal has been investigated by neutron spectroscopy. The lowest magnetic exchange stiffness constant D of 97±2 meV Å² has been found in the cubic austenite phase. In the two martensitic phases the exchange stiffness constants are significantly larger with values of 149±4 meV Å² in the tetragonal phase and 198±7 meV Å² in the low temperature martensite. The large value of D in the low temperature phase compared to the other phases cannot be explained solely by renormalization effects due to magnon-magnon interaction and is attributed to a stronger magnetic coupling. In both the martensitic phases a gap of magnon excitation at the Γ-point of about 0.2 meV was observed.     

Line intensities of acetylene: New measurements in the 1.5-μm spectral region and global modelling in the ΔP=10 series

Using the Fourier transform spectra of the acetylene molecule recorded near 1.5-μm, the intensities of 111 lines belonging to seven hot bands of the main isotopologue ¹²C₂H₂ have been retrieved by means of a multispectrum fitting procedure. Considering the density of lines in the spectra, and the fact that the measured bands are the weakest observed, the accuracy of the measurements is around 10%. At first stage, an empirical treatment of these data has been performed, leading to the vibrational transition dipole moment squared and some Herman–Wallis coefficients. Then the measured line intensities of this work and collected ones from the literature have been treated simultaneously within the framework of the effective operator approach.     

Investigation of the local structure and the effects of the orbit reduction factor on the EPR g-factors for octahedral (CrO6) cluster in TiO2:Cr and MgO:Cr systems

A theoretical method for studying the inter-relation between electronic and molecular structure has been proposed based on the complete energy matrices for a d³ configuration ion in a tetragonal ligand-field. By means of this method, the local structure for Cr³⁺ ion doped in oxides TiO₂ (anatase) and MgO has been determined. The calculated results indicate that the local structure of the (CrO₆)⁹⁻ cluster in TiO₂:Cr³⁺ and MgO:Cr³⁺ systems exists as a compressed distortion relative to the regular octahedron. Meanwhile, the dependence of the EPR zero-field splitting parameter D on the local structure parameter ΔR (ΔR=R₁−R₂) has been revealed. In addition, the relation between the EPR g-factors (g,g,Δg) and the orbit reduction factor k has been discussed for the two systems, suggesting that the orbit reduction factor k is very important to understand the EPR g-factors.     

Collapse of the magnetic ordering and structural anomalies in the U La S system: neutron diffraction and specific heat measurements

We report specific heat and neutron diffraction measurements of seven samples in the solid solution system U_xLa_1-xS. All samples have the simple fcc NaCl crystal structure. Both specific heat and neutron diffraction confirm the suggestion from the earlier magnetic measurements that the ferromagnetism disappears abruptly at 0.57. Near there is a doubling of the electronic contribution to the specific heat, as compared to the value of 23 mJ mol^-1K^-2 in pure US. Around the widths of the nuclear Bragg peaks show a considerable broadening, as well as anomalies in the mean lattice parameter, as compared to those expected from Vegard's law. A preliminary analysis suggests this broadening may be due to a loss of long range lattice order near . However, these changes are independent of temperature, so that further experiments are necessary before they can be associated with the changes in magnetic behavior at . Received 18 September 1998     

Effect of side by side interactions on the thermodynamic properties of adsorbed CO molecules on the Ni(111) surface: a cluster model study

The effect of electrostatic interactions on vibrational frequencies and thermodynamic properties of CO adsorbate on the Ni(111) surface is calculated by taking the first and second nearest-neighbour interactions into account. In order to obtain reasonable results, the cluster model of various surface adsorption sites with CO adsorbate is partially optimized, using Density Functional Theory and also the MP2 method for the hcp site. Comparison between DFT and MP2 results shows that DFT results are more reliable for this system. The stretching and bending frequencies of CO adsorbate are calculated using both Partial Hessian Analysis and Cluster–Adsorbate Coupling methods. Stretching and bending frequencies are both shifted by the side by side interactions. The coupling of surface phonons and adsorbate vibrations reduces the side effects. The largest side effects on the vibrational internal energy, isochoric heat capacity, entropy and total Helmholtz free energy of adsorbed CO molecule calculated using the CAC method are found for 0.5 ML coverage. The results of the CAC method are better, but the PHA method can be used as a simple upper bound estimation. The adsorptive phase acts as an intelligent material in such a way that it changes its configuration in order to reduce the side effects.     

Effect of pH on the uptake of arsenate and vanadate by hydrotalcites in alkaline solutions: a Raman spectroscopic study

Hydrotalcites have been synthesised using solutions of three different pH values to assess the effect of pH on the uptake of arsenate and vanadate. The ability of these hydrotalcites to remove vanadate and arsenate from solution has been determined by inductively coupled optical emission spectroscopy. Raman spectroscopy was used to monitor changes in the anionic species for hydrotalcites synthesised at different pH values. The results show a reduction in the concentration of arsenate and vanadate anions that are removed in extremely alkaline solutions. Hydrotalcites containing arsenate and vanadate are stable in solutions up to pH 10. Exposure of these hydrotalcites to higher pH values results in the removal of large percentages of arsenate and vanadate from the hydrotalcite interlayer. Copyright © 2010 John Wiley & Sons, Ltd.     

High-resolution LIF measurements on hyperfine structure and isotope shifts in various states of Lu I using the second and third harmonic of a cw Ti:sapphire laser

With the second and third harmonic of a tunable single-mode cw Ti:S laser, generated inside external enhancement cavities, high-resolution LIF measurements on several states of Lu I in various parts of the electromagnetic spectrum are performed. From these measurements, hyperfine structure A and B constants for both ¹⁷⁵Lu and ¹⁷⁶Lu as well as isotope shifts have been determined for all levels observed in the single-step excitation process. From the measured A constants, the magnetic hyperfine structure anomaly has been derived for various states. Received 14 January 2002 Published online 19 July 2002     

Adsorption structure and spin polarization of pentacene on a magnetized Fe(1 0 0) substrate: SPMDS and ERDA study

The adsorption structure and spin-resolved electronic structure of pentacene on Fe(1 0 0) surfaces were investigated using elastic recoil detection analysis (ERDA) and spin-polarized metastable deexcitation spectroscopy (SPMDS), respectively. It was found that the pentacene molecule adsorbs with its molecular plane parallel to the surface in the initial stage of growth, while the molecular plane tilted from the surface with the increase of the coverage. In the pentacene-Fe surface interaction, a donation and backdonation interaction was indicated. It was found that the polarity of the spin polarization induced in the pentacene molecular orbitals was opposite to each other between the orbitals contributing to the donation and those contributing to the backdonation.     

Effects of T2-relaxation in MAS NMR spectra of the satellite transitions for quadrupolar nuclei: a 27Al MAS and single-crystal NMR study of alum KAl(SO4)2.12H2O

Asymmetries in the manifold of spinning sidebands (ssbs) from the satellite transitions have been observed in variable-temperature 27Al MAS NMR spectra of alum (KAl(SO4)2.12H2O), recorded in the temperature range from -76 to 92 degrees C. The asymmetries decrease with increasing temperature and reflect the fact that the ssbs exhibit systematically different linewidths for different spectral regions of the manifold. From spin-echo 27Al NMR experiments on a single-crystal of alum, it is demonstrated that these variations in linewidth originate from differences in transverse (T2) relaxation times for the two inner (m=1/2<-->m=3/2 and m=-1/2<-->m=-3/2) and correspondingly for the two outer (m=3/2<-->m=5/2 and m=-3/2<-->m=-5/2) satellite transitions. T2 relaxation times in the range 0.5-3.5 ms are observed for the individual satellite transitions at -50 degrees C and 7.05 T, whereas the corresponding T1 relaxation times, determined from similar saturation-recovery 27Al NMR experiments, are almost constant (T1=0.07-0.10 s) for the individual satellite transitions. The variation in T2 values for the individual 27Al satellite transitions for alum is justified by a simple theoretical approach which considers the cross-correlation of the local fluctuating fields from the quadrupolar coupling and the heteronuclear (27Al-1H) dipolar interaction on the T2 relaxation times for the individual transitions. This approach and the observed differences in T2 values indicate that a single random motional process modulates both the quadrupolar and heteronuclear dipolar interactions for 27Al in alum at low temperatures.     

Effect of local structure on electron paramagnetic resonance spectra for trigonal [Cr(H2O)6]3+coordination complex in the sulfate alums series: a ligand field theory study

A simple theoretical method is introduced for studying the interrelation between electronic and molecular structures.By diagonalizing the 120 × 120 complete energy matrices,the relationships between zero-field splitting(ZFS) parameter D and local distortion parameter △θ for Cr 3+ ions doped,separately,in α-and β-alums are investigated.Our results indicate that there exists an approximately linear relationship between D and △θ in a temperature range 4.2-297 K and the signs of D and △θ are opposite to each other.Moreover,in order to understand the contribution of spin-orbit coupling coefficient ζ to ZFS parameter D,the relation between D and ζ is also discussed.     

Study of the corrosion products formed on a multiphase CuAlBe alloy in a sodium chloride solution by micro-Raman and in situ AFM measurements

The corrosion products formed on a multiphase Cu-11.40Al-0.55Be (wt.%) alloy in 3.5% NaCl at open circuit potential, and their evolution with immersion time were studied mainly by micro-Raman and in situ AFM measurements. The aluminium content of each phase affects the formation of the corrosion products on them. After 1 day of immersion, γ₂ precipitates were more susceptible to dealuminization, while α′ phase exhibited a high corrosion stability. The corrosion products evolved with immersion time, and CuCl₂ and a Cu₂O/CuO double layer film were the stable products formed on all the phases after long times.     

High-resolution resonant photoemission study of the 4f states in a typical Kondo system: CePd3

We exploited resonant photoemission at the Ce absorption edge to investigate the Ce 4f states in . High resolution spectra reveal, near the Fermi level, the characteristic fine structure of intermediate valence Ce compounds. The spectral lineshape is consistent with the typical “Kondo” character of CePd, but the prominent ionization peak is found at the unusually low binding energy of 1 eV. We briefly discuss the implications of these observations. Received: 13 October 1997 / Accepted: 21 January 1998     

Nanomechanics of single silkworm and spider fibres: a Raman and micro‐mechanical in situ study of the conformation change with stress

The combination of micro‐Raman spectroscopy and an advanced universal fibre tester (UFT) made it possible to probe at the nanoscale (through monitoring the modification of chemical bonds) the change in conformation (α‐helix, β‐sheet, etc.), macromolecular fibroin chain orientation and coupling during the application of stress, quantitatively. Different single fibres of silkworms (Bombyx mori, Gonometa rufobrunea, Gonometa postica) and a spider (Nephila madagascariensis) were tested in a dry environment and compared with the behaviour of keratin fibre. As observed previously for single keratin fibres, a direct relationship is observed between nano‐ and micro‐mechanical tensile behaviour. The phase transition plateau, well defined for some pristine B. mori fibres, disappears in degummed fibres, which indicates a structural modification and increasing disorder with chemical treatments. Stress‐controlled micro‐Raman analysis shows that a few modes involving CH₂ and/or amide groups of β‐conformation chains undergo a wavenumber softening during the elastic behaviour (∼0–3%), although most of the modes are not affected. A different behaviour is observed for modes associated with ‘ordered’ and ‘disordered’ β‐sheets and helical chains. Larger softening is observed for lattice modes with increasing stress/strain, as expected. Structural changes and relationships with mechanical behaviour are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

"RLC串联电路暂态过程的研究"实验中电容系统误差的测量与修正

在"RLC串联电路暂态过程的研究"实验中,由于示波器两测量探头间电容和电容箱"零电容"的存在,导致阻尼振荡周期的理论计算值与实验值之间可能产生非常大的误差.本文通过测量上述两类电容,对周期的理论计算值进行了修正,使之与实验值的相对误差明显减小.