NMR Detection of Phase Transition in a ZSM-5 Silicalite Caused by the Adsorbed Hexane and Decane Molecules

Times of longitudinal T _1b and transverse T _2b magnetic relaxation of hexane and decane molecules in micropores of ZSM-5 silicalite were measured as functions of the content of these liquid n-alkanes in zeolite and of temperature. The stepwise changes in the T _1b and T _2b times were revealed in the region of 8% content of hydrocarbons. The observed changes in the concentration and temperature dependences of T _1b and T _2b times are explained by the rearrangement of silicalite crystal lattice under the action of adsorbed molecules.     

Geometrical restrictions of water diffusion in aqueous protein systems. A study using NMR field-gradient techniques

Geometrical restrictions of water diffusion in different aqueous protein systems were studied using two versions of the NMR field gradient technique. The samples were aqueous systems of bovine serum albumin, gelatin and horse myoglobin at concentrations ranging from diluted solutions to almost dry powders being only partly hydrated. Hydrated protein aerogels were produced by the aid of a special preparation procedure and studied in addition. The experiments referred to the, temperature and concentration dependences of the water diffusion coefficient above and below the free-water freezing temperature. The diffusion coefficient within clusters of overlapping hydration shells is reduced by one order of magnitude compared with that of bulk water. Geometrical restrictions manifest themselves (a) by the obstruction effect observed at low protein concentrations, (b) by the topologically two-dimensional diffusion in the network of overlapping hydration shells, (c) by the percolation threshold appearing at about 15%_b.w. water and (d) by the anomalous diffusion behaviour concluded from the protein aerogel study.     

Structural and dynamic properties of polyoxyethylene sorbitan monooleate micelle in water dispersion studied by pulsed field gradient NMR

The diffusion phenomenon of a nonionic surfactant, polyoxyethylene sorbitan monooleate (POE-SMO), micelle in aqueous solution was investigated by pulsed field gradient nuclear magnetic resonance (PFG NMR) with a high gradient strength of 17.4 T/m at the diffusion timet _d varied from 3 to 300 ms. This high gradient strength allowed us to measure the slow self-diffusion coefficient of POE-SMO micelle, and the short diffusion time below 10 ms showed the restricted diffusion of the micelle. At the shortt _d the self-diffusion of the micelle was restricted and the restricted sizes were 1.8, 1.5, and 0.8 μm for the POE-SMO concentration of 100, 200 and 300 mM, respectively, and 0.6 μm for the POE-SMO only. The possible reason of this restriction was assumed to be the formation of a spatial network or a micellar clustering. Furthermore, a proton exchange between water molecule and surfactant OH group on the micelle surface was proposed. With respect to this proposal, the residence time of the proton at the micelle surface and the thickness of the surface were investigated from proton self-diffusion coefficients by PFG NMR.     

NMR and X-ray diffraction studies of the influence of adsorbed molecule nature on phase transitions in a ZSM-5 silicalite

Pulsed NMR and X-ray diffraction analysis are employed to study the influence of adsorbed toluene, p-xylene, acetone, and di(ethylene glycol) (DEG) molecules on phase transitions in a ZSM-5 silicalite. In the region of phase transitions, times T₁ and T₂ of longitudinal and transverse magnetic relaxation of apolar molecules adsorbed in silicalite micropores increase and decrease in a jumpwise manner, respectively, with a rise in the total content of the liquid. Such changes in T₁ and T₂ occur for hexane, decane, toluene, and p-xylene molecules. Qualitatively different concentration dependences of T₁ and T₂ are observed for polar acetone and DEG molecules, because these liquids do not cause a earrangement in the crystal lattice of silicalite; this is confirmed by the X-ray diffraction data.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 802–806.Original Russian Text Copyright © 2004 by Pimenov, Skirda, Maksimenko, Morozov, Opanasyuk.     

NMR magnetization transfer as a tool for characterization of nanoporous materials

The application of nuclear magnetic resonance magnetization transfer experiments to probe the surface-to-volume ratio and pore morphology of porous materials with characteristic pore sizes of 1-100 nm is described. The method is based on the phenomenon of incomplete freezing of liquids in small pores where a few monolayers adjacent to the pore walls remain liquid. Sufficient difference between the transverse relaxation times in the solid frozen core and liquid surface layer allows the initial preparation and subsequent re-equilibration of a solid-liquid magnetization grating. The method is demonstrated using model nanoporous materials with known characteristics. The ensuing problems of the mechanism of the magnetization transfer through the interface and within the frozen core are discussed and elucidated by pulsed-field-gradient NMR experiments.     

Water self-diffusion in Chlorella sp. studied by pulse field gradient NMR

The water self-diffusion behavior in chlorella water suspension was investigated by pulsed field gradient NMR technique. Three types of water was determined, which differs according to the self-diffusion coefficients; bulk water, extracellular and intracellular water. Intracellular and extracellular water self-diffusion were restricted, and the sizes of restriction regions were 3.4 microm and 17 microm, respectively. The water molecular exchange process between these three diffusion regions was investigated. The residence time and exchange rate constant for chlorella cells were obtained. The cell wall permeability determined from the rate constant as 3 x 10(-6) m/s agreed with the permeability 10(-6) m/s obtained from time dependence of intracellular water self-diffusion coefficient. The structural cluster model of chlorella cell is estimated to describe the extracellular water self-diffusion in chlorella water suspension.     

Optical charge transfer for the dope in GaAs<Cr>

It is concluded that the chromium dope is amphoteric in behavior on the basis of the spectra, kinetics, and lux-ampere characteristics of the absorption and photoconductivity induced by 1.15-μm IR laser radiation in high-resistance specimens of GaAs〈Cr〉. It is assumed that the additional IR illumination produces optical charge transfer in the chromium in accordance with Cr³⁺3d³ + hν → Cr²⁺3d⁴ + Cr⁴⁺3d². The photoneutralization of the Cr⁴⁺3d² centers is responsible for additional optical-absorption and photoconductivity bands appearing in the long-wave region. The kinetic equations for these centers are solved, which describes the experimental results satisfactorily. It is suggested that chromium may compensate not only shallow donors in GaAs but also shallow acceptors.     

Spatial structure of peptides determined by residual dipolar couplings analysis

The gated decoupled (13)C NMR spectra of a dipeptide (Glu-Trp) and a tetrapeptide (NAc-Ser-Phe-Val-Gly-OMe) were recorded in D(2)O and in a lyotropic alignment medium (pentaethylene glycol monododecyl ether/n-hexanol). The residual dipolar couplings were extracted as the differences between the observed couplings for the magnetic nuclei dissolved in the latter and former media. Using a computational optimization, the spatial structures of the compounds were calculated starting from their respective low energy conformations obtained on a semiempirical basis. The uniformity of each conformation was confirmed by the solid-state (13)C NMR spectra of powder samples. Differences between the starting structures and final ones, optimized when employing residual dipolar couplings, are discussed.     

The Low-Field Pulsed Mode Dynamic Nuclear Polarization in the Pentavalent Chromium Complex and Crude Oils

Measurements of the enhancement of the proton resonance signal right after applying the radiofrequency pulse with the variable duration in the magnetic field of about 100 Gauss on the homebuilt prototype of the dynamic nuclear polarization (DNP) spectrometer at near room temperature are presented. A dependence of the DNP enhancement of the solvent protons of the solution of the pentavalent chromium complex in ethylene glycol on the pumping pulse duration and incident pumping power is given. No DNP effect on the native protons of the crude oils and natural bitumen from the Russian oilfields is observed. A miserable DNP enhancement is registered on the protons of toluene by dissolving the crude oil and bitumen samples. The perspectives of using the results and technical solutions for geological exploration, studies of the asphaltene structures and their dynamics are discussed.