EPR study of carbonate derived and ozonide radicals in carbonated apatites synthesized from aqueous solutions

In this study, a series of Na⁺ and¹²CO ₃ ^2? containing apatites synthesized by a hydrolysis of octo-calciumphosphate (OCP) and dried at 25°C until constant weight, were examined with EPR after X-irradiation. A variety of different paramagnetic radicals was formed, giving rise to composite and hence complex EPR powder spectra. The spectra were successfully decomposed into their basic components using a multivariate statistical technique. The different components could be identified unambiguously. In this way, it was found that an O^?, an O ₃ ^? , a CO ₃ ^? , two types of CO ₂ ^? and two types of CO ₃ ^3? ions were formed upon X-irradiation. Also resonances from atomic hydrogen were observed. The most striking feature is the presence of the ozonide ion, which is only rarely observed in irradiated hydroxyapatites. A comparison is made between the EPR spectra of apatite samples prepared by hydrolysis of OCP on the one hand, and those of samples prepared by hydrolyzing monetite, and the tooth enamel spectrum on the other hand.     

1H and31P ENDOR of the isotropic CO2 − signal atg=2.0007 in the EPR spectra of precipitated carbonated apatites

The isotropic EPR signal atg=2.0007 in X-irradiated carbonated apatites, precipitated from aquaeous solutions and dried at 25°C, is investigated with Electron Nuclear Double Resonance (ENDOR). The²³Na,³¹P and¹H ENDOR results indicate that the precursor of this radical is most probably located in an aqueous phase entrapped between the crystallites (the so-called occluded water). Other experimental features, such as the correlation between the appearance of the signal in the EPR spectrum and the presence of some residual (adsorbed and/or occluded) water in the sample seem to strengthen our hypothesis.     

Electrochromic properties of tungsten oxides synthesized from aqueous solutions

Tungsten oxides are known to exhibit interesting electrochemical properties. Ion insertion (Li⁺, H⁺) within the oxide network is highly reversible. It leads to a blue coloration and WO₃ thin films can be used as electrochromic layers in display devices or smart windows. Tungsten oxide thin films can be conveniently deposited from aqueous solutions of tungstic acid. However polytungstic acids are not stable and tend to precipitate into hydrated tungsten oxide WO₃⋅2H₂O. The condensation of polytungstic species can be chemically controlled by adding foreign ions in the solution. Precipitation is no more observed in the presence of H₂O₂. Peroxopolytungstic acids are formed in which chelating [O₂]²⁻ ligands prevent the formation of an oxide network. Such solutions are specially convenient for the deposition of optically transparent thin films. Mixed oxides WO₃-MoO₃ are obtained when condensation is performed in the presence of Mo⁶⁺ cations. This paper shows how the condensation of tungstic acid can be chemically controlled and describes the electrochemical properties of the films deposited from such solutions. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Characterization of free radicals from vitamin K1 and menadione by 2 mm-band EPR,ENDOR and ESEEM

The anion and cation radicals of vitamin K₁ and its analog menadione were characterized using the magnetic resonance techniques of Electron Nuclear Double Resonance (ENDOR), Electron Spin Echo Envelope Modulation (ESEEM), and Electron Paramagnetic Resonance (EPR) at X-band and 2 mm-band. Theg-factor anisotropy of the radicals at 2 mm-band allow them to be distinguished from each other in the solid state. Theg-factor matrix of the radical anion of vitamin K₁ is virtually identical with that reported for the reduced A₁ acceptor in green plant photosystem I thus demonstrating that reduced A₁ is the anion radical of vitamin K₁.     

1H NMR study of water relaxation and self-diffusion in human serum albumin aqueous solutions

Summary Water proton spin-lattice relaxation and self-diffusion in aqueous solutions of human serum albumin have been studied by¹H NMR as a function of the protein concentration. Spin-lattice relaxation data, which display a nonlinear behaviour with the protein concentration, could be fitted with a two-phase model taking into account the experimentally determined hydration (?bound?) water values. Despite a similar trend is registered for the water self-diffusion coefficient, such a model has been found unable to explain the related experimental data taken as a function of the biomolecule concentration. On the other hand, the solute-induced proton self-diffusion decrease could be satisfactorily interpreted by postulating an enhanced probability of hydrogen-bond formation occurring within the ?vicinal? water surrounding the biomolecules for several hydration shells. The consistency within the two models is discussed in connection with the magnetic interactions occurring within the solute-solvent systems.     

1H AND 31P NMR of Cat Optic Nerve

The ³¹P and ¹H NMR spectra of perchloric acid extracts of cat optic nerve were obtained. Nerves were exposed by lateral orbitotomy, frozen in situ with liquid nitrogen, removed, and extracted.

Resonances from the high energy phosphates adenosine triphosphate and phosphocreatine, and compounds of phospholipid metabolism, such as phosphorylcholine, phosphorylethanolamine, and their glyceryl esters, were observed and assigned in the ³¹P spectrum. The ³¹P spectrum of cat optic nerve ex vivo also was obtained. Resonances from numerous low-molecular-weight compounds including creatine, N-acetyl-aspartate (NAA), inositol, choline, and various amino acids were observed in the ¹H spectrum and assigned by comparison to the spectra of model compounds. The neurotransmitter N-acetylaspartylglutamate (NAAG), previously found in retinal ganglion cells and implicated in the transmission of visual information, was resolved from NAA and observed for the first time by NMR in tissue extracts at a level higher than that of NAA.     

ESR and ENDOR of free radicals in X-irradiated barbituric acid

Free radicals from dihydrate and dideuterate crystals and from anhydrous powder of barbituric acid X-irradiated between 77 K and room temperature have been studied by ESR and ENDOR spectroscopy. Four different species were characterized. In dihydrate crystals, small amounts of molecular anions were found to be formed in addition to the major radical which results from elimination of a hydrogen from the C(₅)-methylene group. The α-hydrogen coupling in the latter as well as its weak intra- and intermolecular proton interactions were investigated in detail by ENDOR. The cation of barbituric acid was observed in dideuterate crystals between 77 K and 130 K. Isothermal decay curves indicated its transformation into the deuterated analog of the R₂Ċ(₅)-H fragment upon warming. The dose-yield relationship of dihydrate and anhydrous powder suggested a stabilization of this radical via interaction with the crystal water. Both the transformation and the stabilization mechanisms were supported by ENDOR-findings on weakly coupled protons.     

Iterative reconstruction of radially-sampled 31P bSSFP data using prior information from 1H MRI

The purpose of this study is to improve direct phosphorus (³¹P) MR imaging. Therefore, 3D density-adapted radially-sampled balanced steady-state free precession (bSSFP) sequences were developed and an iterative approach exploiting additional anatomical information from hydrogen (¹H) data was evaluated. Three healthy volunteers were examined at B₀ = 7 T in order to obtain the spatial distribution of the phosphocreatine (PCr) intensities in the human calf muscle with a nominal isotropic resolution of 10 mm in an acquisition time of 10 min. Three different bSSFP gradient schemes were investigated. The highest signal-to-noise ratio (SNR) was obtained for a scheme with two point-reflected density-adapted gradients. Furthermore, the conventional reconstruction based on a gridding algorithm was compared to an iterative method using an ¹H MRI constraint in terms of a segmented binary mask, which comprises prior knowledge. The parameters of the iterative approach were optimized and evaluated by simulations featuring ³¹P MRI parameters. Thereby, partial volume effects as well as Gibbs ringing artifacts could be reduced. In conclusion, the iterative reconstruction of ³¹P bSSFP data using an ¹H MRI constraint is appropriate for investigating regions where sharp tissue boundaries occur and leads to images that represent the real PCr distributions better than conventionally reconstructed images.     

Interactions between polyamines and nucleotides studied by31P and1H NMR

The formation of complexes between poly- and mono-amines and some polyphosphate molecules such as ATP, ADP and tripolyphosphate was studied by³¹P and¹H NMR. Evidence for formation of complexes was obtained by¹H NMR, while the values of dissociation constants of the complexes between nucleotides and spermine and spermidine, calculated from the shift of the³¹P NMR, were in mM range.     

Estimation of the specific surface area of apatites in human mineralized tissues using 31P MAS NMR

Specific surface areas of apatites in whole human mineralized tissues were estimated from (31)P MAS NMR linewidths: 77 m(2)g(-1) for enamel and 94 m(2)g(-1) for dentin, dental cementum and cortical bone.     

有机磷化合物的NMR研究——Ⅱ0,0-二烷基膦酸酯的1H、13C和31PNMR谱

本文报道了21个0,0一二烷基膦酸酯类化合物的¹H、¹³C和³¹P NMR参数。研究和讨论了不等价的二烷基¹H、¹³C化学位移和磷碳偶合常数与立体化学的关系。测定了(CH₃CH₂O)₂P(O)CH(CH₂NO₂)(p-OCH₃C₆H₄)的¹³C自旋一晶格弛豫时间T₁,二乙基¹³C T₁间的差别,说明在类似化合物中,含有化学位移各向异性对弛豫的贡献。     

Molecular dynamics of n-dodecylammonium chloride in aqueous solutions investigated by 2H NMR and 1H NMR relaxometry

Molecular dynamics in n-dodecylammonium chloride/water solutions for concentrations of 34 and 45 wt% was studied by 2H NMR and by 1H NMR dispersion of spin-lattice relaxation in the 2 kHz-90 MHz frequency range. The system exhibits a number of lyotropic liquid crystalline phases, which differ in symmetry and involve motions characterized by a wide frequency scale. The analysis of 2H NMR lineshapes of selectively deuterated DDACl molecules gave us an evidence for local trans-gauche conformational changes in the chains, whereas the dispersion of spin-lattice relaxation times T1 explored by fast field cycling method revealed fast local motions, translational diffusion and collective molecular dynamics of the chains. In particular, we have found that the order director fluctuation mechanism in smectic and nematic phases dominates spin-lattice relaxation below 1 MHz and that local motions and translational diffusion are responsible for the spin-lattice relaxation in the higher Larmor frequency range.     

Interleaved 1H and 31P spectroscopic imaging for studying regional brain injury

We present a new approach for in vivo localized spectroscopy which combines 1H and 31P one-dimensional spectroscopic imaging pulse sequences in an interleaved, time-shared manner using a surface coil. This approach was used to acquire metabolic information from a rat brain with regional ischemia at 4.7 Tesla. Spectra with very good signal-to-noise ratios, void of chemical shift artifacts, are obtainable from voxel sizes less than 0.3 cm3 in 40 min. Advantages and drawbacks of the proposed methodology are discussed.     

Raman identification of H2CO in aqueous solutions

Aqueous formaldehyde solutions of mole fraction from 0.05 to 0.20 were studied by Raman spectroscopy at temperatures up to 180 °C. The previously unreported Raman spectrum of formaldehyde under its non‐hydrated form H₂CO has been identified, in addition to the already known bands from methanediol CH₂(OH)₂ and poly(oxymethylene)glycols HO(CH₂O)_nH formed by hydration and subsequent polymerization of the formaldehyde molecules. The experimental spectrum of formaldehyde in solutions agrees perfectly with the theoretical calculations. Copyright © 2010 John Wiley & Sons, Ltd.     

Use of 1H/23Na and 1H/31P double frequency tuned birdcage coils to study in vivo carbon tetrachloride-induced hepatotoxicity in rats.

In vivo 1H and 23Na magnetic resonance imaging (MRI) and 31P magnetic resonance spectroscopy (MRS) techniques were used to study CCl4-induced acute hepatotoxicity in rats in situ. One or two hours following exposure to CCl4, a localized edematous region was detected in the liver by 1H MRI. The CCl4-induced edema was localized in a region surrounding the hepatic portal vein. With the use of a 23Na/1H double frequency tuned bird-cage imaging coil an increase in Na+ ion flux was also observed in the same region as the edematous region detected by 1H-MRI. Pretreatment with alpha-phenyl-tert-butyl nitrone (PBN), a free radical spin trap, 30 min prior to CCl4 exposure, was found to reduce the CCl4-induced edematous response in the liver observed in either 1H or 23Na-NMR images. Inhibition of the CCl4-induced edematous response in rat liver by PBN demonstrates that free radical intermediates, arising from the metabolism of CCl4, are possibly the key causal agents in the initiation of the edematous response. In addition, with the use of a 31P/1H double frequency tuned bird-cage imaging/spectroscopy coil, localized 31P spectra (ISIS) were obtained from the regions of CCl4-induced "tissue damage" observed in the 1H-MRI images. The most notable changes observed from the 31P spectra were an increase in inorganic phosphate (Pi) and a decrease in hepatocytosolic pH in the CCl4-treated rat livers in comparison to saline-treated control livers.     

Incoherent quasielastic neutron scattering from H2O and aqueous ZnCl2 solutions

A study of the diffusive motions of the protons in pure water and ZnCl₂ aqueous solutions has been performed, using incoherent quasielastic neutron scattering. It is shown that it is essential to take into account the rotational motion of the water molecules. The translational linewidth is conveniently fitted over the whole Q-range, using the Random Jump Diffusion model for which the jump length turns out to be roughly the same for pure H₂O and the saturated solution, fairly close to the distance between protons in the water molecule.