NMR studies of structure and dynamics in fruit cuticle polyesters

Cutin and suberin are support polymers involved in waterproofing the leaves and fruits of higher plants, regulating the flow of nutrients among various plant organs, and minimizing the deleterious impact of microbial pathogens. Despite the complexity and intractable nature of these plant biopolyesters, their molecular structure and development are amenable to study by suitable solid-state and solution-state NMR techniques. Interactions of tomato cutin with water were examined by solid-state 2H and 13C NMR, showing that water films enhance rapid segmental motions of the acyl chains and are associated with a fivefold increase in surface elasticity upon cutin hydration. The suberization of wounded potato tissues was studied by solid-state 13C NMR, revealing the likely phenylpropanoid structures that permit dense cross-linking of the suberin structure and their proximity to the cell-wall polysaccharides. Finally, two new approaches were developed to elucidate the molecular structures of these biopolymers: partial depolymerization followed by spectroscopic analysis of the soluble oligomers; and swelling of the intact materials followed by magic-angle spinning (MAS) NMR analysis.     

Angular divergence of forwards and backwards emission from an FIR laser,using a pyroelectric vidicon

The angular divergence of FIR radiation at 66 μm and 116 μm from a D₂O cell pumped by single mode pulsed CO₂ laser is obtained, in both forward and backward directions. The forward emission, in similarity with SRS at other wavelengths, emerges with divergence close to the diffraction limit in some cases. The backward emission, probably dominated by ASE, has a greater divergence and at high filling pressures appears to break up into speckles.     

13C high-resolution solid state NMR studies of the structure and dynamics of 1,6:3,4-dianhydro-2-O-tosyl-beta-D-galactopyranose

13C CP/MAS, dipolar dephasing MAS and theoretical GIAO calculations were employed to assign 13C resonances to the molecular structure of 1,6:3,4-dianhydro-2-O-tosyl-beta-D-galactopyranose 1. From spinning sideband intensities, employing the graphical method of Herzfeld and Berger the 13C delta(ii) parameters for aromatic residue were calculated. The experimental data were compared with computed results obtained by means of the B3PW91 hybrid method and 6-311G (df, p) basis set. The X-ray geometry of 1 with the correlated position of hydrogen atoms was taken as input data for theoretical calculations. As concluded from Cambridge Crystallographic Database (CSD) search, there are two reports describing the X-ray studies of 1 that show the slightly different geometry of the compound under investigation. This work shows that such discrepancies in geometry can generate differences between computed 13C delta(ii) parameters up to 6 ppm. 13C T1 and 1H T1rho relaxation times reveal that 1 is very rigid in crystal lattice. This structure is characterized by extremely long 1H T1rho, found to be in range ca. 200 ms.     

NMR and NQR studies of spin dynamics and superconductivity in High-T c oxides

The magnetic and superconducting properties in the high-T _c cuprates have been investigated over a wide hole doping range by⁶³Cu,¹⁷O and²⁰⁵Tl NMR and NQR in the lightly-doped La_2?xSr_xCuO₄ (LSCO), the heavily-doped Tl₂Ba₂CuO_6+y (TBCO) and the Zn-doped YBa₂Cu₃O₇ (YBCO₇). In low doping region, the large antiferromagnetic (AF) spin correlation around the zone boundary (q=Q) causes the Curie-Weiss behavior of⁶³(1/T ₁ T) associated with that of the staggered susceptibility χ_O(T) in LSCO. In the vicinity of the hole content whereT _c has a peak, the AF spin correlation still survives, although the magnetic coherence length ξ_M is considerably short being presumably (ξ_M/a) ～ 1. The further doping destroys progressively the AF spin correlation, which is no longer present is non-superconducting TBCO compounds. These NMR evidences signify that there is an intimate relation between the presence of the AF spin correlation and the onset of the superconductivity. The local collapse of AF spin correlation is a primary cause for the unexpected strong reduction ofT _c in case of the substitution of Zn impurities into the CuO₂ plane. The superconducting properties clarified by NMR experiments cannot be accounted for by the conventional BCS model or other isotropic s-wave models. A d-wave model is applicable in interpreting consistently most of the NMR results, if the finite density of states at the Fermi level is taken into consideration and is associated with the pair breaking effect. There are increasing evidences that the magnetic mechanism for the superconductivity is promising in high-T _c cuprates.     

Temperature-dependent protein backbone dynamics from auto- and cross-correlated NMR relaxation rates

The temperature dependence of nuclear magnetic resonance relaxation rates was investigated for the backbone of¹⁵N/¹³C labeled human ubiquitin in the temperature range of 20–50 °C. The¹⁵N autorelaxation rates give evidence that the potential energy functions for¹⁵N?H^N bonds are not quadratic, in agreement with results for other proteins. Cross-correlation rates arising from correlated fluctuations of two¹⁵N?H^N dipole-dipole interactions involving successive residues were obtained by the method of Pelupessy et al. (P. Pelupessy, S. Ravindranathan, G. Bodenhausen: J. Biomol. NMR 25, 265–280, 2003). The results suggest the presence of slow internal motions at 50 °C.     

2H T2rho relaxation dynamics and double-quantum filtered NMR studies

In this study 2H T2rho DQF NMR spectra of water in MCM-41 were measured. The T2rho double-quantum filtered (DQF) NMR signal is generated by applying a radio frequency (RF) field for various durations and then observed after a monitor RF pulse. It was found that the transfer between different quantum coherences by the couplings during long-duration RF fields (i.e., soft pulses) and that residual quadrupolar interaction dominates the signal decay. Knowledge of coherence transfer during long-RF pulses has special significance for the development of sophisticated multi-quantum NMR experiments especially multi-quantum MRI applications.     

WIM/WISE NMR studies of chain dynamics in solid polymers and blends

Wideline separation (WISE) NMR with window-less isotropic mixing (WIM) is developed as a method to study the dynamics of polymers and blends. This experiment is designed to measure the dynamics of polymers through the proton lineshapes that are correlated with the carbon chemical shifts in two-dimensional NMR experiments. If the atoms experience large amplitude fluctuations that are fast compared to the dipolar broadening, then the proton lines will be narrowed relative to rigid solids. We have modified the WISE experiment by replacing the cross polarization step with WIM to quench spin diffusion during the cross polarization so that the proton linewidths can be directly related to the chain dynamics. Two-dimensional WIM/WISE has been used to measure the main-chain and side-chain dynamics in poly(n-butyl methacrylate) and blends of polystyrene and poly(vinyl methyl ether).     

Host and impurity NMR studies in CoGa alloys - a cluster spin glass system

The Co_x Ga_1-x alloys having CsCl structure contain nonmagnetic Co and Ga atoms (host) and magnetic Co atoms (impurities) for x ? 0.50. We report here the simultaneous observation of the applied field NMR of host nuclei and the zero field resonance (ZFR) of impurity nuclei. From the ac susceptibility measurements and the field dependence of ZFR signals we conclude that for 0.50 ? × ? 0.64, this system is a “cluster spin glass”.