NMR relaxation studies of GdDTPA in human serum albumin solution

The water relaxation enhancement behavior of GdDTPA in human serum albumin (HSA) solution has been studied. The results indicate that GdDTPA can integrate noncovalently with HSA, mainly in forms of (GdDTPA)HSA and (GdDTPA),HSA, for which the apparent equilibrium constants are 0.05 mM(-1) and 0.02 mM(-2), respectively. (C) 1999 Elsevier Science Ltd. All rights reserved.

A HIGH-RESOLUTION SOLID-STATE NMR AND DSC STUDY OF MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF POLY(VINYL ALCOHOL)/POLY(N-VINYL-2-PYRROLIDONE) BLENDS

Blends of crystallizable poly(vinyl alcohol) (PVA) with poly(N-vinyl-2-pyrrolidone) (PVPy) were studied by C-13 cross-polarization/magic angle spinning (CP/MAS) n.m.r. and d.s.c. The C-13 CP/MAS spectra show that the blends were miscible on a molecular level over the whole composition range studied, and that the intramolecular hydrogen bonds of PVA were broken and intermolecular hydrogen bonds between PVA and PVPy formed when the two polymers were mixed. The results of a spin-lattice relaxation study indicate that blending of the two polymers reduced the average intermolecular distance and molecular motion of each component, even in the miscible amorphous phase, and that addition of PVPy into PVA has a definite effect on the crystallinity of PVA in the blends over the whole composition range, yet there is still detectable crystallinity even when the PVPy content is as high as 80 wt%. These results are consistent with those obtained from d.s.c. studies.

LOCAL MAIN-CHAIN DYNAMICS OF PHENOLPHTHALEIN POLYETHERSULFONE

Local main chain dynamics of dissolved phenolphthalein polyethersulfone (PES-C) in solution with chloroform-d(1) were examined through C-13 NMR relaxation measurements. Spin-lattice relaxation times and NOE (nuclear Overhauser effects) factors were measured as a function of temperature. The relaxation data were interpreted in terms of main chain segmental motion by using the damped orientational diffusion model (DAMP) and the conformation jump model (VJGM) derived by Valeur, Jarry, Geny, and Monnerie. The simulation method used is N-SIMPLEX, which gives, in this study, a result of the object function less than 10(-4). Correlation times were obtained for the main chain motion of PES-C with these models and the results indicate that the main chain of PES-C are flexible. The comparison between PES-C and 1,2-polybutadiene is proposed. The distribution of the correlation time for the main chain motion by using VJGM model is discussed. The temperature dependence of correlation times for PES-C indicating the dynamical rigidity of its chains is obtained.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

NMR studies of Gd(DTPA-BIN) in human serum albumin solution

Stable gadolinium complexes, such as Gd(DTPA) and Gd(DOTA), are usually used as the contrast agents for magnetic resonance imaging(MRI). Reported here are the enhanced relaxation properties of a novel gadolinium complex, diethylene-triaminopentaacetate Lis (isoniazid) [Gd(DTPA-BIN)], in aqueous and in human serum albumin(HSA) solution, which indicates that (1) two Gd(DTPA-BIN) can integrate non-covalently with one HSA with an equilibrium constant of 0. 02 mmol(-2) . L-2 ; (2) the relaxivities are 3. 28 and 4. 92 mmol(-1) . L . s(-1) for the free Gd(DTPA-BIN) and the [Gd(DTPA-BIN)](2), HSA conjugator, respectively; (3) the rotational correlation time of protein conjugator is notably higher than that of the free complex, The above results may imply that Gd(DTPA-BIN) has a higher tissue selectivity than that of its parent Gd(DTPA).

NMR investigation of phenolphthalein polyether ether ketone .1. The chain structure and assignments of H-1, C-13 NMR lines of PEK-C

Amorphous samples of polyether ketone with cardo(PEK-C) have been studied in the solution state by C-13, H-1 high-resolution NMR, The H-1 and C-13 1D NMR spectra were assigned using two dimensional chemical shift correlated spectroscopy, 2D homonuclear correlated(COSY) and heteronuclear correlated (HETCOR) spectroscopy present important information. In this work, the structural units of PEK-C was determined by NMR. For some peaks, these assignments are confirmed by two dimensional long-range heteronuclear correlation experiments, A little modification is made on the original C-13 peak assignments for the main chain, The symmetry and the isotacticity of the chain structure for PEK-C are obvious on NMR data.

C-13 NMR study on the aqueous structure of lanthanide citrate complexes

The aqueous complexation of lanthanide complexes of citrate in pH 7.4 solutions has been studied by using lanthanide-induced shift and relaxation times measurement methods. These results indicate that citrate coordinate via 3-hydroxyl and 3-carboxylate groups with lanthanide ions and form 1:2 (Ln/cit) isostructural complexes through lanthanide series. We suggest a new coordination geometry which is different from that described in literature.

NMR Spectra of polyimides: Interpretation and local chain motion study

Three kinds of high-performance polyimides 1 (poly(ketone-imide) PKI), 2 (poly(ether-imide) PEI) and 3 (poly(oxy-imide) POI) were studied using nuclear magnetic resonance (NMR). The NMR spectra of the polyimides were assigned according to the comprehensive consideration of the substitution effect of different substituting groups, viz. distortionless enhancement by polarization transfer (DEPT), no nuclear Overhauser effect (NNE), analysis of relaxation time, and two-dimensional correlated spectroscopy (COSY) techniques. The structural units of these three polyimides were determined. Carbon-13 and proton relaxation times for PEI and PKI were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (JS model) and anisotropic group rotation such as phenyl group rotation and methyl group rotation. Correlation times for the main-chain motion are in the tens of picosecond range which indicates the high flexibility of polyimide chains. Correlation times for phenyl group and methyl group rotations are more than 1 order of magnitude lower and approximately 1 order of magnitude higher than that of the main chain, respectively.

A NMR-STUDY OF THE INTERACTION OF SILICA WITH DIPALMITOYLPHOSPHATIDYLCHOLINE LIPOSOMES

The interaction of silica with dipalmitoylphosphatidylcholine (DPPC) liposomes has been studied by detecting H-1 and 2D NOESY NMR spectra and measuring proton spin-lattice relaxation time (T-1). The antagonistic effect of aluminium citrate on silica has also been studied by measuring the proton T-1 values, The results show that silica particles mainly bind to the phosphate moiety of the polar headgroup of DPPC bilayers through hydrogen bonds between Si-OH and O-P groups, but they have no significant effect on the conformation of the choline group of the polar headgroup, The addition of silica particles decreases the mobilities of the hydrocarbon chains slightly, Proton T-1 data also indicate that aluminium citrate reduces the effect of silica, A possible mechanism for the toxicity of silica and the antagonistic effect of aluminium titrate on silica is suggested. (C) 1995 Academic Press Inc.

MICROSTRUCTURE ANALYSIS OF 3 SEGMENTED COPOLYMERS CONTAINING POLYDIMETHYLSILOXANE BY SOLID-STATE HIGH-RESOLUTION NMR

The microstructure of two bicomponent and one tricomponent segmented copolymers, based on polydimethylsiloxane, poly(p-hydroxystyrene) or/and polysulfone, were investigated using an extended Goldman-Shen pulse sequence, proton spin-spin relaxation measurements, and C-13 and Si-29 NMR spectra. The results indicate that there exist four phases with different sizes, components and morphological structure in the segmented copolymers studied in this work, i. e., a rigid-chain phase of very slow motion, a rigid-chain-rich phase of slow motion, a flexible-chain-rich phase of fast motion and a flexible-chain phase of faster motion. The sizes of different domains, calculated from the spin diffusion rates, are about 50-100 angstrom for the flexible-chain-rich phase of fast motion and 200-300 angstrom for the flexible-chain phase of faster motion. The relative quantities of polydimethylsiloxane in the flexible-chain phase of fast motion are slightly different in different kinds of segmented copolymers.

A HIGH-RESOLUTION SOLID-STATE NMR-STUDY OF THE MISCIBILITY, MORPHOLOGY, AND TOUGHENING MECHANISM OF POLYSTYRENE WITH POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

An extended Goldman-Shen pulse sequence was used to observe indirectly the proton spin diffusion in the blends of polystyrene (PS) with poly(2,6-dimethyl-1,4-phenylene oxides) (PPO). The results indicate that the average distance between PS and PPO is less than 5 angstrom in the intimately mixed phase, but there are heterogeneous domains on a 100-angstrom scale. The data of spin relaxation of carbons, T1(C), for homopolymers and their blends suggest that there is a strong pi-pi electron conjugation interaction between the aromatic rings of PS and those of PPO, while the aromatic rings of PPO drive the aromatic rings of PS to move cooperatively. It is the cooperative motion that markedly improves the impact strength of PS.

Dislocation dynamics of strain relaxation in epitaxial layers

Many experimental observations have clearly shown that dislocation interaction plays a crucial role in the kinetics of strain relaxation in epitaxial thin films. A set of evolution equations are presented in this article. The key feature of the equations

Effect of structural relaxation on deformation behaviour of Zr-based metallic glass

Structural relaxation through isothermal annealing at tempertature below glass transition is conducted on Zr46.75Ti8.25Cu7.5Ni10Be27.5 (Vitreloy-4) bulk metallic glass. Defect concentration is correlated with the annealing time t according to differential scanning calorimetry thermalgrams. The effects of structural relaxation on mechanical properties and deformation behaviour are investigated by using instrumented nanoindentation. It is found that as-cast alloy exhibits pronounced serration flow during the loading process of nanoindentation, and the size and number of serrations decrease with the annealing time. The change of the deformation behaviour with structural relaxation is explained using a free volume model.

Cross-relaxation dynamics on anomalous saturation processes in low pressure supersonic cw HF chemical laser amplifier

It is assumed that both translational and rotational nonequilibrium cross-relaxations play a role simultaneoulsy in low pressure supersonic cw HF chemical laser amplifier. For two-type models of gas flow medium with laminar and turbulent flow diffusion mixing, the expressions of saturated gain spectrum are derived respectively, and the numerical calculations are performed as well. The numerical results show that turbulent flow diffusion mixing model is in the best agreement with the experimental result.

Investigation on Nonequlibrium Radiation and Relaxation Phenomena in Shock Tubes

The experimental results for the excited time of the nonequlibrium radiation and the ionization behind strong shock waves are presented. Using an optical multichannel analyzer, InSb infrared detectors and near-free-molecular Langmuir probes, the infrared radiation, the electron density of air and the nonequilibrium radiation spectra at different moments of the relaxation process in nitrogen test gas behind normal shock waves were obtained, respectively, in hydrogen oxygen combustion driven shock tubes.