Proton Dynamics in Letovicite, (NH4)3H(SO4)2: A H and N NMR Spectroscopic Study

The improper ferroelastic phase letovicite (NH₄)₃H(SO₄)₂ has been studied by ¹H MAS NMR as well as by static ¹⁴N NMR experiments in the temperature range of 296–425 K. The ¹H MAS NMR resonance from ammonium protons can be well distinguished from that of acidic protons. A third resonance appears just below the phase transition temperature which is due to the acidic protons in the paraelastic phase. The lowering of the second moment M₂ for the ammonium protons takes place in the same temperature range as the formation of domain boundaries, while the signals of the acidic protons suffer a line narrowing in the area of T_c. The static ¹⁴N NMR spectra confirm the temperature of the motional changes of the ammonium tetrahedra. Two-dimensional ¹H NOESY spectra indicate a chemical exchange between ammonium protons and the acidic protons of the paraphase.     

Separation of cross-relaxation and exchange in two-site spin systems without resolved couplings

Variable temperature two-dimensional nuclear Overhauser enhancement experiment (2-D NOESY) is used to extract the rate constants and cross-relaxation rates that contribute to the same cross-peaks in NOESY spectra. Rate constants (k _AB) and cross-relaxation rates (R _AB) for two-site spin systems are related to the ratio between the cross-peak and diagonal peak integrals (F) by the expression:R _AB -k _AB = (1/2τ _m)ln[(1 -F)/(1 +F)], where τ_m is the mixing time. As a model, we investigated the exchange processes in a system of dimer calix[4]arenes of C_4v symmetrical configuration with guest inclusion (benzene or benzene-d₆), where the measurement of exchange processes is hindered by the presence of strong nuclear Overhauser enhancement between protons in adjacent aromatic rings in the cone conformation of the calix[4]arene.     

“Quasi-Planck” spectra of capillary turbulence on the surface of liquid hydrogen

We report the first observation of “quasi-Planck” spectra of capillary turbulence on the surface of liquid hydrogen in the dissipation domain. Capillary waves have been driven by low-frequency random force. We have observed that the frequency spectrum of surface elevation changes its dependence from power-like 〈|η_ω²|〉 ∼ ω^−2,8 at middle-frequency domain to “quasi-Planck” distribution ∼e ^ω/ω _d at higher frequencies. The frequency ω _d is proportional to the boundary frequency between inertial interval and dissipation domain and it is scaled up with the increase of driving force.     

Transitions and Spin Dynamics at Very Low Temperature in the Pyrochlores Yb2Ti2O7 and Gd2Sn2O7

An orientational disorder of the cation in [(PyO)D][AuCl₄] crystal was investigated by the ³⁵Cl NQR and ¹H NMR measurements. A structural phase transition was found at ca. 70 K from the temperature dependence of the NQR frequencies both in [(PyO)D][AuCl₄] and [(PyO)H][AuCl₄]. Temperature dependence of the spin-lattice relaxation time T ₁ of the NQR of [AuCl₄]⁻ could be interpreted by an electric field gradient modulation due to the motion of the cation. Characteristics of T ₁ of ³⁵Cl NQR as well as that of ¹H NMR suggest a dynamic orientational disorder of the cation.     

Suppression of Diagonal Peaks in TROSY-Type H NMR NOESY Spectra of N-Labeled Proteins

A novel method for suppression of diagonal peaks in the amide region of NOESY NMR spectra of ¹⁵N-labeled proteins is presented. The method is particularly useful for larger proteins at high magnetic fields where interference between dipolar and chemical shift anisotropy relaxation mechanisms results in large TROSY effects, i.e., large differences in ¹H^N linewidths depending on the spin state of attached ¹⁵N nuclei. In this limit the new TROSY NOESY method does not compromise sensitivity. It is demonstrated using a perdeuterated ¹⁵N-labeled protein sample, Neural Cell Adhesion Molecule 213–308 (NCAM) from rat, in H₂O at 800 MHz.     

Decay of transient nutation in two-level spin systems

This paper reports the results of an experimental study of the decay of transient NMR nutations in a two-level spin system with homogeneous line broadening. The NMR nutation signals in glycerin were studied for 10⩽ω ₁ T ₂⩽150, where ω ₁=γH ₁, with γ the gyromagnetic ratio and H ₁ the amplitude of the magnetic component of the radio-frequency field, and T ₂ is the transverse relaxation time. It is found that in a high-power field (ω ₁ T ₂≫1) the nutation decay rate is independent of ω ₁ and is quantitatively described by Bloch’s model. The data is compared with the data on non-Bloch (ω ₁-dependent) EPR-nutation decay in quartz (R. Boscaino, F. M. Gelardi, and J. P. Corb, Phys. Rev. B 48, 7077 (1993)). Zh. éksp. Teor. Fiz. 111, 1207–1213 (April 1997)     

Assignment of the 1H and 13C Spectra of 5-Methylthio-4H-1-(p-R1-phenyl)-3a-(p-R2-phenyl)-3a,4-dihydro (1,2,4) oxadiazolo(4,5-a), 1,5-benzodiazepines using 2D NMR Spectroscopy.

The ¹H NMR spectra of the title benzodiazepines derivatives is highly congested because all the protons are in aromatic enviroment so many proton signals remain overlap even 300 MHz or higher fields. With this in mind, the assignment of the ¹H and ¹³C spectra of these compounds obtained using COSY, NOESY, HMQC and HMBC experiments is reported.     

Assignment of the 1H and 13C Spectra of 5-Methylthio-4H-1-(p-R1-phenyl)-3a-(p-R2-Phenyl)-3a, 4-dihydro (1,2,4) oxadiazolo(4,5-a), 1, 5-benzodiazepines Using 2D NMR Spectroscopy

The ¹H NMR spectra of the title benzodiazepines derivatives is highly congested because all the protons are in aromatic environment so many proton signals remain overlap even 300 MHz or higher fields. With this in mind, the assignment of the ¹H and ¹³C spectra of these compounds obtained using COSY, NOESY, HMQC and HMBC experiments is reported.     

Structure and lithium ionic conduction mechanism in La4/3−yLi3yTi2O6

The solid solutions La_4/3−yLi_3yTi₂O₆ (y=0.09∼0.33) have been studied by complex impedance spectroscopy, X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) methods. The ionic conductivity shows a maximum value at around y=0.21, and keeps high values at high y concentrations. The XRD patterns show a single phase for all concentration. The crystal structure is orthorhombic with space groupPmmm for y=0.09∼0.15 and tetragonal with space groupP4/mmm for y=0.17∼0.33. The⁷Li static NMR spectra show a main central peak with a Lorenzian shape for y=0.09∼0.21. The central peak is divided into two parts for y=0.23∼0.33. The narrow intense peak is a mobile component due to mobile ions, and a small broad central peak is due to less mobile lithium ions which contribute to immobile component. The⁷Li MAS NMR spectra show negative chemical shifts which decrease with increasing y concentration. In this paper, we discuss the conduction mechanism and the structure from the analysis of conductivity, lattice parameters, occupation, atomic positions and the⁷Li static/MAS NMR spectra.     

Assignments of Nonexchangeable Proton Resonances and the Solution Structures of d–TGGGT

In this paper, we report the studies of the solution structures of synthetic pentadeoxyribonucleotide d-TGGGT(NH₄ ⁺ salt) using 2D–NMR. The 1H–NMR experiments with different temperatures and concentrations reveal an equilibrium between single strand and aggregation. In the experimental condition(22°C, 13mmol/ L), the cross peaks in the COSY spectrum are mainly from single strand, and the spin systems of sugar resonances of this component can be assigned. In contrast, the cross peaks in the NOESY spectrum mainly come from aggregation and the sequential assignments of bases, sugar 1′, 2′ and 2″ protons can be carried out. From NOE connectivities, it is obvious that the aggregation adopts a right–handed helix conformation. It is suggested that the aggregation in our experiment corresponds to the tetramolecular complex.     

Crystalline Aluminium Borates with the Mullite Structure: A <Superscript>11</Superscript>B and <Superscript>27</Superscript>Al Solid-State NMR Study

²⁷Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were acquired at 8.45, 14.1 and 16.45 T for a series of aluminium borates with the mullite structure (Al_6−x B _x O₉, where x has nominal values of 1 to 4) augmented with ²⁷Al multiple-quantum MAS NMR spectra at 8.45 T. Even though the ²⁷Al NMR spectra are complex, simulation of the combined set of data produced a relatively well-defined set of parameters (e.g., quadrupolar interaction, isotropic chemical shift, etc.) for each site. The ¹¹B MAS NMR spectra of the same compounds were also acquired at 14.1 T. Linear changes in the X-ray a-, b- and c-cell parameters with composition suggest that these compounds constitute a continuous series. Based on a Rietveld structural refinement of the compound synthesized as Al₄B₂O₉, the resulting site occupancies and relative site distortions allow the identification of particular sites with specific NM resonances. Changes in the ²⁷Al and ¹¹B MAS NMR spectra of the related compounds with x = 1–4 show at the lowest Al contents a greater degree of asymmetry in the Al sites of the octahedral chains. A fairly distorted cross-linking tetrahedral site, which persists throughout the composition range, is accompanied in the lower Al compositions by two 5-fold coordinated Al–O units which are replaced by two more-regular tetrahedral Al–O sites as the Al content increases. In the compounds of lowest Al composition (i.e., highest B content) both the tetrahedral and trigonal cross-linking sites are distinguishable, but as the Al content increases, the BO₄ units progressively disappear. Authors' address: Kenneth J. D. MacKenzie, School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington, New Zealand     

Carbon-13 Assignments and Revision of the Stereostructures of the Cadinanes 2-Hydroxy-8α-angeloyloxycalamenene and 2-Hydroxy-8α-hydroxycalamenene

The two known cadinanes 2-hydroxy-8α-hydroxycalamenene and 2-hydroxy-8α-angeloyloxycalamenene were isolated from a Louisiana population of Heterotheca subaxillaris.

Their ¹³C NMR spectra were fully assigned by the application of HETCOR, COLOC, COSY, NOESY and DEPT experiments. It was shown on the basis of NOESY experiments that both cadinanes require revision at the stereogenic centre C-7.     

ωN final state interactions and ω-meson production from heavy-ion collisions

We calculate the elastic and inelastic ωN→ωN, →πN, →ρN, →ρπN, →ππN, →σN reactions within a boson exchange approximation where the ωρπ coupling constant and form factor are fixed by the reaction πN→ωN in comparison to the experimental data. We find rather large ωN cross sections at low relative momenta of the ω-meson which leads to a substantial broadening of the ω-meson width in nuclear matter. The implications of the ωN final state interactions are studied for ω production in ¹²C +¹²C, ⁴⁰Ca +⁴⁰Ca and ⁵⁸Ni +⁵⁸Ni reactions at about 2 · A GeV within the HSD transport approach; the drastic changes of the transverse mass spectra relative to a general m _T-scaling (for π⁰ and η mesons) might be controlled experimentally by the TAPS Collaboration. Received: 28 April 1999 / Revised version: 7 June 1999     

NMR STUDIES ON ANTINEOPLASTIC ANTIBIOTICS AD-32 AND DM

AD-32和DM是蒽环类抗肿瘤抗生素,临床上用于治疗难治性膀胱癌、淋巴瘤、间皮瘤、乳癌、卵巢癌、头颈部癌、小细胞肺癌、睾丸癌、骨髓癌、结肠癌、血管肉瘤、子宫颈癌、肝癌等.本文在进行AD-32和DM的化学合成和工艺研究的基础上,应用     

A New Method of Obtaining Structural Information from 2M Exchange NMR and NQR Spectra of Powders

A method of calculating the singularities of two-dimensional correlation spectra of powders and determining the structural parameters with the help of a computer program is described. The opportunities of the method are illustrated on examples of experimental 2M exchange ¹³ C NMR spectra of dimethylsulfone, 2M exchange ² H NMR spectrum of hexamethylbenzene, and model 2M exchange nutational NQR spectrum for spin I = 3/2. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 72–75, August, 2005.     

New polarization effect and collective excitation in S = 1/2 quasi-one-dimensional antiferromagnetic quantum spin chain

Anomalous polarization characteristics of magnetic resonance in CuGeO₃ doped with 2% Co impurity are reported. For the Faraday geometry, this mode is damped for the microwave field B _ω aligned along a certain crystallographic direction, showing that the character of magnetic oscillation differs from the standard spin precession. The observed resonance coexists with the ESR on Cu²⁺ chains; it is argued not to be caused by “impurity” EPR, as previously claimed, but to correspond to a previously unknown collective mode of magnetic oscillations in an S = 1/2 AF quantum spin chain. The text was submitted by the authors in English.     

Topological and physical effects of rotation and spin in the general relativistic theory of gravitation

Interrelations of the intrinsic momentum (spin), rotation of material distributions, and intrinsic momentum of the gravitational field are investigated in the context of the general relativistic theory of gravitation involving the general relativity theory (GRT) and the Einstein-Cartan theory. It is demonstrated that the spin density vector of the gravitational field s _g ⁱ is equal to the rotor of the tetrad reference point ωⁱ=ɛ^iklm e _k ^(a) e_(a)l,m/2 to within the factor 1/κ (s _g ⁱ =ω/κc). It is demonstrated that the vector s _g ⁱ is proportional to the spin density vector of the gravitating field sⁱ (ω)=jc(Ψγⁱγ₅Ψ)/2 as well as the pseudovector of space-time torsion Qⁱ in the Einstein-Cartan theory, which in both cases induces a cubic nonlinearity of the spinor field. An expression for the energy-momentum density tensor of the eddy gravitational field is derived. It is also demonstrated that the free eddy gravitational field with polarized spin can form “mole holes.” An ideal fast-rotating self-gravitating fluid can cause a similar effect. The corresponding exact solutions of joint systems of the Einstein and rotating ideal fluid equations are presented. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 57–60, October, 2007.     

The transient EPR spectra and spin dynamics of coupled three-spin systems in photosynthetic reaction centres

The concept of introducing an additional, stable paramagnetic species into photosynthetic reaction centres to increase the information content of their spin polarized transient EPR spectra is investigated theoretically. The light-induced electron transfer in such systems generates a series of coupled three-spin states consisting of sequential photoinduced radical pairs coupled to the stable spin which acts as an “observer”. The spin polarized transient EPR spectra are investigated using the coupled three-spin system P⁺I⁻Q⁻ _A in pre-reduced bacterial reaction centres as a specific example which has been studied experimentally. The evolution of the spin system and the spin polarized EPR spectra of P⁺I⁻Q⁻ _A and Q⁻ _A following recombination of the radical pair (P = primary donor, I = primary acceptor, Q_A = quinone acceptor) are calculated numerically by solving the equations of motion for the density matrix. The net polarization of the observer spin is also calculated analytically by perturbation theory for the case of a single, short-lived, charge-separated state. The result bears a close resemblance to the chemically induced nuclear polarization (CIDNP) generated in photolysis reactions in which a nuclear spin plays the role of the observer interacting with the radical pair intermediates. However, because the Zeeman frequencies of the three electron spins involved are usually quite similar, the polarization of the electron observer spin in strong magnetic fields can reflect features of the CIDNP effect in both, high and low magnetic fields. The dependence of the quinone spin polarization on the exchange couplings in the three-spin system is investigated by numerical simulations, and it is shown that the observed emissive polarization pattern is compatible with either sign, positive or negative, for a range of exchange couplings, J_PI, in the primary pair. The microwave frequency and orientation dependence of the spectra are discussed as two of several possible criteria for determining the sign of J_PI.     

Iterative Lineshape Fitting of MAS NMR Spectra: A Tool to Investigate HomonuclearJCoupling in Isolated Spin Pairs

Possibilities and limitations of iterative lineshape fitting procedures of MAS NMR spectra of isolated homonuclear spin pairs, aiming at determination of magnitudes and orientations of the various interaction tensors, are explored. Requirements regarding experimental MAS NMR spectra as well as simulation and fitting procedures are discussed. Our examples chosen are the isolated³¹P spin pairs in solid Na₄P₂O₇· 10H₂O, (1), and Cd(NO₃)₂· 2PPh₃, (2). In both cases the two³¹P chemical shielding tensors in the molecular unit are related byC₂symmetry, and determination of the orientations of these two tensors in the molecular frame is possible. In addition, aspects of homonuclearJcoupling will be addressed. For 1, both magnitude and sign of²J_iso(³¹P,³¹P) (J_iso= −19.5 ± 2.5 Hz) are obtained; for 2, (J_iso= +139 ± 3 Hz) anisotropy ofJwith an orientation of theJ-coupling tensor collinear, or nearly collinear, with the dipolar coupling tensor can be excluded, while absence or presence of anisotropy ofJwith any other relative orientation of theJ-coupling tensor cannot be determined.     

Direct Determination of Motional Correlation Times by 1D MAS and 2D Exchange NMR Techniques

One- and two-dimensional static and magic-angle spinning (MAS) exchange NMR experiments for quantifying slow (τ_c> 1 ms) molecular reorientation dynamics are analyzed, emphasizing the extent to which motional correlation times can be extracteddirectlyfrom the experimental data. The static two-dimensional (2D) exchange NMR experiment provides geometric information, as well as exchange time scales via straightforward and model-free application of Legendre-type orientational autocorrelation functions, particularly for axially symmetric interaction tensors, as often encountered in solid-state²H and¹³C NMR. Under conditions of MAS, increased sensitivity yields higher signal-to-noise spectra, with concomitant improvement in the precision and speed of correlation time measurements, although at the expense of reduced angular (geometric) resolution. For random jump motions, one-dimensional (1D)exchange-inducedsidebands (EIS)¹³C NMR and the recently developed ODESSA and time-reverse ODESSA experiments complement the static and MAS two-dimensional exchange NMR experiments by providing faster means of obtaining motional correlation times. For each of these experiments, the correlation time of a dynamic process may be obtained from a simple exponential fit to the integrated peak intensities measured as a function of mixing time. This is demonstrated on polycrystalline dimethylsulfone, where the reorientation rates from EIS, ODESSA, time-reverse ODESSA, and 2D exchange are shown to be equivalent and consistent with literature values. In the analysis, the advantages and limitations of the different methods are compared and discussed.