Proton spin relaxation of molecules adsorbed in NaY and NaPtY zeolite; The influence of adsorbed water on the distribution of atomic platinum

The longitudinal proton spin relaxation time T₁ of molecules adsorbed in commercial zeolites is predominantly caused by paramagnetic impurities, typically of the order of 0.1 wt% of iron. If only 1 wt% of platinum is introduced into the zeolite (as [Pt(NH₃)₄]²⁺), T₁ of water is enhanced up to one order of magnitude, as was shown in a preceding paper. The reason for this effect is that, under suitable thermal pretreatment of the Pt-exchanged zeolite, the Pt²⁺ ions are reduced by the ammonia to atomic platinum and part of the Pt atoms migrate preferentially to Fe³⁺ ions. Thus, Fe³⁺ ions, controlling T₁, are covered and up to 90% of paramagnetic sites for water is occupied by Pt atoms. In this paper, it is shown that Pt atoms preferentially migrate to Fe³⁺ ions only under the influence of water and that, therefore, various adsorbed organic molecules do not show the enhancement of T₁, unless the NaPtY zeolite is suitably pretreated with water before the organic molecules are adsorbed.     

General features of proton longitudinal relaxation in proteins in solution

Time courses of the recovery upon nonselective inversion of all individual proton magnetizations in several globular proteins in aqueous (²H₂O) solution were calculated for varying degrees of rotational correlation time of the molecule (10⁻⁹ s ∼ ∞) and compared with the experimental data on various proteins at 400 MHz. In the calculation, the spinrelaxation mechanism was assumed to be solely the dipolar interaction between protons, and the three-site random jumps of the methyl groups, along with the rotation of the whole molecule, were taken into account. The following conclusions were drawn. ( 1 ) For proteins whose molecular weights are below ∼ 10,000, whole-molecule rotation is a dominant source of relaxation, and the longitudinal relaxation times may vary considerably from proton to proton. (2) For proteins whose molecular weights are above ∼20,000, methyl group rotations assisted by spin diffusion are common and major sources of relaxation, producing T₁ values close to 1 s. In the intermediate region (molecular weight 10,000 ∼ 20,000), both whole-molecule rotation and methyl group rotations contribute significantly to relaxation. (3) In some proteins, segmental motions are as important as methyl group rotations in determining relaxation rate.     

Indication from NMR of Grotthuss mechanism for proton conduction in H2Sb4O11·nH2O

We have measured the second moment, the linewidth and the relaxation times T₁ and T₂ of the ¹H magnetic resonance signal from 4.2 to 380 K in the fact proton conductors H₂Sb₄O₁₁·nH₂O. Our results reveal that the high ionic conductivity of these materials is due to a Grotthuss-type proton diffusion mechanism with succession of molecular reorientations of H₃O⁺ ions or H₂O molecules and of proton jumps from H₃O⁺ to H₂O.     

Nuclear magnetic relaxation of <Superscript>3</Superscript>He in contact with an aerogel above the Fermi temperature

The spin kinetics of ³He in an aerogel has been studied above the Fermi temperature. The magnetic relaxation times T ₁ and T ₂ of adsorbed, gaseous, and liquid ³He in a 95% silica aerogel at a temperature of 1.5 K have been determined as functions of frequency by means of pulse nuclear magnetic resonance. It has been found that the time T ₁ is linear in frequency in all three cases, whereas T ₂ is independent of frequency. To explain the observed behavior of the longitudinal relaxation rate, a theoretical model of relaxation in the adsorbed layer of ³He taking into account the filamentary structure of the aerogel is proposed.     

X-band Electron Spin Relaxation Times for Four Aromatic Radicals in Fluid Solution and Comparison with Other Organic Radicals

X-band electron spin relaxation times of BDPA (1:1 α,γ-bisdiphenylene-β-phenylallyl), galvinoxyl 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy, DPPH (2,2-diphenyl-1-picrylhydrazyl) and thianthrene radicals in fluid solution were measured by electron spin echo and inversion recovery at ambient temperature. Tumbling correlation times are estimated to be in the range of 20–30 ps. In this fast tumbling regime T ₁ ~ T ₂. Relaxation times are compared with previously reported values for symmetrically substituted triarylmethyl, semiquinone, and nitroxide radicals. The concentration dependence of spin lattice relaxation for neutral BDPA in toluene is about 10³ times greater than for anionic trityl radicals in water. T ₁ decreases in the order carbon-center BDPA > galvinoxyl > DPPH > thianthrene. The dominant relaxation mechanisms are proposed to be a local mode for BDPA, spin rotation, local mode and modulation of anisotropic proton hyperfine coupling for galvinoxyl, modulation of anisotropic nitrogen hyperfine for DPPH, and spin rotation plus modulation of anisotropic proton hyperfine coupling for thianthrene.     

13C NMR investigation of adsorbed hydrocarbons

By means of Fourier transform techniques ¹³C nmr spectra and longitudinal ¹³C magnetic relaxation times of various butene isomers sorbed on NaY and NaX zeolites have been studied. In contrast to ¹H resonance where only two broad lines can be observed, the ¹³C spectra show separated sharp lines. The shift Δσ = σ_ads-σ_free of the carbon-13 lines of adsorbed molecules with respect to the resonance positions of free molecules and the longitudinal relaxation times indicate a peculiar behaviour of the groups  CH and = C

of the adsorbed n-butene and isobutene molecules, respectively. The resonance deviations Δσ to lower fields in these groups decrease in the order isobutene (δσ = ? 10.3 ppm), but-1-ene (δσ ≈ ?5.7 ppm) and but-2-enes (Δσ ≈ ? 2.2–2.4 ppm), whereby the spectra of cis-but-2-ene and trans-but-2-ene show similar differences as found in the liquid state. When adsorbed on NaY and NaX types (silica/alumina ratios 5 and 3.5) the ¹³C nmr line positions of but-1-ene molecules are the same within the limits of experimental error, which demonstrates that electrostatic fields have no noticeable influence on the molecular parameters in these systems. Therefore one may conclude that chemical bonds to Na⁺ cations have the dominant effect on the line shift Δσ. CNDO-MO calculations based on such a model have shown that a charge transfer occurs from the π-electrons and the electrons of the methyl group hydrogen atoms to the cation.     

Estimation of water content and water mobility in the nucleus and cytoplasm of Xenopus laevis oocytes by NMR microscopy

NMR microscopy is a noninvasive approach for studying cell structure and properties. Spatially resolved measurement of the relaxation times T₁ and T₂ provided information on the water proton spin density and water mobility in different parts of Xenopus laevis oocytes. The spin-lattice relaxation time T₁ was determined using a saturation-recovery sequence and the common spin-echo sequence with increasing repetition times, while the transverse relaxation time T₂ was measured by means of the spin-echo sequence with varying echo times. From the relaxation times, the mole fractions of possible reorientational correlation times τ_c for different types of intracellular water were calculated according to a simple two-phase model. The values for T₁, T₂, and proton spin density (i.e., water content) are: nucleus ⪢ animal cytoplasm > vegetal cytoplasm. Based on the estimation of τ_c, nearly 90% of the nuclear water and 74.4% of the water of the animal pole was considered as free mobile water, whereas 55.5% of the water of the vegetal pole appeared as bound water.     

Magnetic properties of Heisenberg triangular antiferromagnet V15 cluster studied by NMR

The magnetic properties of an s?=?1/2 Heisenberg triangular antiferromagnet V15 have been studied by proton nuclear magnetic resonance (NMR) at very low temperature down to 100 mK using a He³-He⁴ dilution refrigerator. In total spin S _T?=?3/2 ground state above 2.7 Tesla, proton spin-lattice relaxation rate (1/T₁) shows thermally activated behavior as a function of temperature. On the other hand, a temperature independent behavior of 1/T₁ at very low temperatures is observed in frustrated S _T?=?1/2 ground state below 2.7 Tesla. Possible origins for the peculiar behavior of 1/T₁ will be discussed in terms of magnetic fluctuations due to spin frustration.     

Proton diffusion in the room-temperature phase of [(NH4)1−xRbx]3H(SO4)2 as studied by 1H spin-lattice relaxation in the rotating frame

Proton diffusion in the room-temperature phase (phase II) of [(NH₄)_1?xRb_x]₃H(SO₄)₂ (0≤x≤1) has been studied by means of ¹H spin-lattice relaxation times in the rotating frame, T_1ρ. The ¹H T_1ρ values were measured at 200.13 MHz in the range of 380–490 K. The ammonium protons and the acidic protons have independent T_1ρ values in the higher temperature range of phase II, suggesting that the spin diffusion between the two species is ineffective. The translational diffusion of the acidic protons is the most dominant mechanism to relax both the ammonium protons and the acidic protons in phase II. The ¹H T_1ρ values in phase II are analyzed theoretically and the motional parameters are obtained. The results of NMR well explain the macroscopic proton conductivity.     

Proton spin relaxation in the system NaPtY zeolite/water; the state of platinum

In commercial zeolites the longitudinal proton spin relaxation time T₁ of adsorbed molecules is predominantly caused by paramagnetic impurities (0.07 wt% of iron in the starting NaY zeolite). Only 1 wt% of platinum, introduced as [Pt(NH₃)4]²⁺, enhances T₁ of water up to one order of magnitude, depending on the thermal pretreatment of the exchanged zeolite. In connection with the behaviour of the transverse relaxation time T₂ and with the mass spectrum of the gases escaping during thermal pretreatment, it is concluded from the strong effect on T₁ that the Pt²⁺ ions are reduced by the ammonia to atomic platinum and that the Pt atoms migrate preferentially to Fe³⁺ ions. Thus, Fe³⁺ ions, controlling T₁, are covered and up to 90% of paramagnetic sites for water are occupied by Pt atoms, whereas in the case of a statistical distribution of the Pt atoms, the probability for a paramagnetic site to be occupied by platinum amounts to 0.1% to 1%. Presumably, the iron species covered are Fe³⁺ ions in cationic sites of the zeolite, as in this case besides dispersion energy $\text{(E}{}_{\mathrm{dis}}\text{≈}\text{kcal}\text{mol}\text{)}$ polarization energy of the pair Pt-Fe³⁺ comes into play, surmounting E_dis by two orders of magnitude.     

Surface-NMR relaxation and echo of aquifers in geomagnetic field

Macroscopic samples of near-surface water in pores or fractures of rocks down to 100 m and deeper are studied by the measurement of proton relaxation and echo in the Earth’s magnetic field. The excitation and reception of the surface nuclear magnetic resonance (SNMR) signal is accomplished with the help of an antenna, circle or 8-shaped (for the minimization of the outer electromagnetic jamming influence), placed at the surface. The frequency of magnetic resonance in the case considered amounts to several kilohertz, the dead time of the instrumentation to several milliseconds. Water in extremely small pores of water-resisting rocks (e.g., in argillaceous grounds), is chemically bound, crystallization or frozen water has smaller times of spin relaxation and is not registered. The distribution of water concentration with depth is determined by inversion of an integral equation, including the model and measured dependences of the SNMR signal against the intensity of excitation. The current state of the art of the SNMR sounding and perspectives of this method on the basis of free induction decay and spin echo detection and relaxation times measurement are presented. Free induction decayT ₂ ^* equal to 60 ms, spin-echoT ₂ equal to 220 ms, and inversion-recoveryT ₁ equal to 700 ms relaxation times have been measured for medium-to coarse-grained sand aquifer. Microscopic characteristics of the aquifer — longitudinal relaxivity (7·10^?3 cm/s), transverse relaxivity (3.5·10^?2 cm/s), and local magnetic field gradient (2·10^?2 G/cm) — have been estimated from experimental data. The importance of spin relaxation and echo measurements for obtaining the information about the microstructure of pores and fractures, as well as filtration, properties of aquifers and diamagnetic, paramagnetic and hydrocarbon contamination, is emphasized.     

Exchange and dipolar spin-spin interaction and rotational diffusion in saturation transfer EPR spectroscopy

Saturation transfer EPR spectroscopy (STEPR) provides a means for investigating weak spin-spin interaction between spin-labelled molecules because the spectral intensity is proportional to the effective spin-lattice relaxation time,T ₁ ^eff. Rate equations for the spin population defferences yield equivalent results for the dependence ofT ₁ ^eff on the physical (or chemical) and Heisenberg spin exchange rates and show thatT ₁ ^eff depends on the extent of redistribution of saturation throughout the anisotropic spin label powder lineshape. This approach yields a particularly simple formulation for the dependence of the STEPR lineshape on slow rotational diffusion. The effects of spin exchange are readily distinguished from those of slow rotational diffusion because of the insensitivity of the STEPR lineshape in the former case. The characteristic dependence of the STEPR spectral intensity on spin concentration allows determination of the exchange rate and can be used for studying slow translational diffusion, e.g. of spin-labelled proteins. Dipolar relaxation induced by paramagnetic ions gives a linear dependence of the reciprocal spin label STEPR intensity on metal ion concentration. STEPR measurements with spin-labelled lipid molecules in gel phase membranes in the presence of Ni²⁺ ions yield reliable distance information and provide calibrations for use with other systems.     

Response of lysozyme internal dynamics to hydration probed by13C and1H solid-state NMR relaxation

We have studied the hydration dependence of the internal protein dynamics of hen egg white lysozyme by naturally abundant¹³C and¹H nuclear magnetic resonance (NMR) relaxation. NMR relaxation timesT ₁, off-resonanceT _1p and proton-decoupled on-resonanceT _1p (only for carbon expriments) were measured in the temperature range from 0 to 50°C. The spectral resolution in carbon cross-polarization magic angle spinning spectrum allows to treat methine, methylene and methyl carbons separately, while proton experiments provide only one integral signal from all protons at a time. The relaxation times were quantitatively analyzed by the well-established correlation function formalism and model-free approach. The whole set of the data could be adequately described by a model assuming three types of motion having correlation times around 10^?4, 10^?9 and 10^?12 s. The slowest process originated from correlated conformational transitions between different energy minima, the intermediate process could be identified as librations within one energy minimum, and the fastest one is a fast rotation of methyl protons the symmetry axis of methyl groups. A comparison of the dynamic behavior of lysozyme and polylysine obtained from a previous study (A. Krushelnitsky, D. Faizullin, D. Reichert, Biopolymers 73, 1–15, 2004) reveals that in the dry state both biopolymers are rigid on both fast and slow time scales. Upon hydration, lysozyme and polylysine reveal a considerable enhancement of the internal mobility, however, in different ways. The side chains of polylysine are more mobile than those of lysozyme, whereas for the backbone a reversed picture is observed. This difference correlates with structural features of lysozyme and polylysine discussed in detail. Due to the presence of a fast spin diffusion, the analysis of proton relaxation data is a more difficult task. However, our data demonstrate that the correlation functions of motion obtained from carbon and proton experiments are substantially different. We explained this by the fact that these two types of NMR relaxation experiments probe the motion of different internuclear vectors. The comparison of the proton data with our previous results on proton relaxation timesT ₁ measured over a wide temperature range indicates that at low temperatures lysozyme undergoes structural rearrangements affecting the amplitudes and/or activation energies of motions.     

Critical nuclear relaxation in cobalt metal

Nuclear magnetic resonance of cobalt metal was investigated in the paramagnetic and ferromagnetic states and in the critical region below T_c. The Knight shift and spin lattice relaxation times were measured in the paramagnetic phase in the solid and liquid states from 1578 K to 1825 K. The resonant frequency, spin-lattice and spin-spin relaxation times were measured in the ferromagnetic phase from room temperature to 1385 K. The main part of (T₁T)^-1 results from fluctuating orbital moments in both phases except near T_c where this process forms the background for critical spin relaxation. The critical exponents for T^-1₁ and for the magnetization in the ferromagnetic state were found to be n' = 0.96 ± 0.07 and β = 0.308 ± 0.012, respectively.     

Proton spin relaxation in hexagonal ice

Measurements of the rotating frame proton spin relaxation timeT _1p in hexagonal ice single crystals as a function of temperature ? for various rotating magnetic field strengths reveal the expectedT _1p minimum at the lowest practicable field values. This allows a very precise determination of the proton correlation (? molecular jump) time τ_c and the related activation energy ΔE by means of the theoretical reasoning of relaxation spectroscopy. We find the Arrhenius-law temperature dependenceτ _c=1.99×10^?17exp(0.603/8.61×10^?5 ?)sec, which is in good agreement with our earlier indirect derivation.     

Zur Definition von Relaxationszeit und Korrelationszeit in magnetischen Resonanzexperimenten

Kubo's general definition of relaxation and correlation times in magnetic spin systems, applicable to non-exponential processes, is evaluated for several non-exponential relaxation and correlation functions known from nmr experiments. The new definition eliminates the arbitrary factors usually encountered in the time constants of nonexponential irreversible processes. For the correlation time of the well-known “translational two-spin model”, three different values are used in the literature; our definition leads toτ _t =1/5 d²/D (d=distance of closest approach between the two spins,D=diffusion coefficient of the related molecules), which is an intermediate value to the conventional abbreviationsτ _t =1/5d ²/D andτ _t =1/6d ²/D.     

Dielectric and proton relaxation from ammonium ion motion in alum

Dielectric losses and proton spin lattice relaxation T₁ and T_1? give identical correlation times in NH₄Al(SO₄)₂ · 12H₂O from 75 to 200 K. This is explained as hopping of NH⁺₄ between two positions with different orientations and electric dipole moments.     

<Superscript>27</Superscript>Al NMR Study of the Structure and Dynamics of Natrolite

The temperature dependences of nuclear magnetic resonance and magic angle spinning nuclear magnetic resonance spectra of ²⁷Al nuclei in natrolite (Na₂Al₂Si₃O₁₀· 2H₂O) have been studied. The influence of water molecules and sodium ions mobility on the shape of the ²⁷Al NMR spectrum and framework dynamics have been discussed The temperature dependences of the spin–lattice relaxation times T₁ of ²⁷Al nuclei in natrolite have also been studied. It has been shown that the spin–lattice relaxation of the ²⁷Al is governed by the electric quadrupole interaction with the crystal electric field gradients modulated by translational motion of H₂O molecules in the natrolite pores. The dipolar interactions with paramagnetic impurities become significant as a relaxation mechanism of the ²⁷Al nuclei only at low temperatures (<270 K).     

Das kritische magnetische Verhalten von EuO

Mössbauer effect and magnetization measurements were employed in order to study the static and especially the dynamic magnetic properties of the nearly Heisenberg ferromagnet EuO near its Curie temperature,T _c=69.2 °K. The critical exponent β of the spontaneous magnetization was determined to be β=0.34±0.02. It was shown that critical slowing down of spin fluctuations takes place nearT _c with spin relaxation times between 7×10^?11 sec (T=1.01T _c) and 1.5×10^?1 sec (T=1.03T _c). The experimental values of the relaxation time were found to be in satisfactory agreement with theoretically computed ones. Just belowT _c the Mössbauer spectra exhibit relaxation effects, which are characteristic for the occurence of critical super-paramagnetism. Investigations of several samples indicated quantitatively, that critical superparamagnetism has its origin in the non ideal composition of the real crystal.     

7Li NMR analysis on perovskite structured Li0.15La0.28TaO3

The nanocrystalline perovskite material Li_0.15La_0.28TaO₃ has been synthesized by alkoxide-free Pechini type sol gel method. ⁷Li NMR measurements were carried out using a Bruker Avance 300 spectrometer at 116 MHz over the temperature range 150 to 400 K. Longitudinal spin-lattice relaxation times (T₁) measured by saturation recovery and longitudinal relaxation times in the rotating frame (T_1ρ) measured using the pulse sequence (π/2–spin lock τ acquisition) with lock radio-frequency field υ = 62.5 kHz and the T₂ relaxation time measured by Hahn echo are presented. The static Hahn-echo spectra show two different lithium sites in this perovskite oxide. Further, the relaxation measurements T₁ and T_1ρ show two different types of lithium cations with fast and slow dynamics.