Complex dynamics of proton and deuteron transfer in double hydrogen bond of benzoic acid isotopes

This paper deals with spin-lattice relaxation due to classical jumps and incoherent tunnelling of protons and deuterons in hydrogen bonds in solids. An analysis of experimental spin-lattice relaxation data for carboxylic acids suggests that tunnelling does not contribute to spin-lattice relaxation above the temperature at which the thermal energy of molecules and the potential barrier height are equal. It is also shown that contributions to the spin-lattice relaxation rate due to classical motion and incoherent tunnelling in excited vibrational states are negligible for fast proton transfer. However, for deuterons this contribution to spin-lattice relaxation is significant.     

Applicability of the method of kinetic equations for describing nuclear quadrupole resonance in molecular crystals

The applicability of the method of kinetic equations for describing nuclear quadrupole resonance (NQR) in molecular crystals is demonstrated for the case in which the relaxation processes are produced by torsional vibrations of the molecules. The Bloch system of equations for NQR spins I=3/2 situated in an axisymmetric electrical field and expressions for spin-lattice relaxation times were obtained.     

Identification of halogen substituents in natural products by measurement of 13c spin-lattice relaxation times and integrated intensities

A method is proposed for differentiating brominated carbons from chlorinated carbons by means of natural-abundance ¹³C NMR spectroscopy. The basis of the method is that the spin-lattice relaxation behaviour of brominated carbons is influenced by carbon-bromine scalar interactions, which can lead to shortened ¹³C spin-lattice relaxation times and reduced values of the nuclear Overhauser enhancement. C-Cl scalar interactions make a negligible contribution to the spin-lattice relaxation of chlorinated carbons. These effects are illustrated by measurement of the ¹³C spin-lattice relaxation times and integrated intensities of chloro-, bromo and iodobenzene and chloro-, bromo- and iodocyclohexane. The method is then tested on four polyhalogenated marine natural products. The results indicate that ¹³C relaxation measurements can be used to distinguish brominated carbons from chlorinated carbons in the case of halogenated quaternary carbons, sp² hydridized methine carbons and some sp³ hydridized methine carbons, but not in the case of halogenated methylene carbons or gem-dihalo substituted methine carbons.     

Arsenic containing heterocycles. II. Confirmation of the structure of benzo[a]-9-chlorophenarsazine 12-chloride by 13C-NMR spectroscopy and spin-lattice relaxation time studies: Possible evidence for the contribution of an 75as-13C mechanism to the relaxation of the arsenic bearing quarternary carbons in the phenarsazine ring system

The product of the reaction of (3-chlorophenyl)-2-naphthylamine with arsenic trichloride has been confirmed to be benzo(a)-9-chlorophenarsazine 12-chloride by ¹³C-nmr spectroscopy and spin-lattice (T₁) relaxation time measurements. A considerable shortening of the spin-lattice relaxation times of the arsenic bearing quaternary carbons, relative to the calculated relaxation times, was observed. This discrepancy has been interpreted in terms of an ⁷⁵As-¹³C dipolar contribution to quaternary carbon relaxation.     

Isotropic hyperfine interaction and spin-lattice relaxation for radicals in the solid state. Part 4

Spin-lattice relaxation is discussed for radicals in a solid with isotropic hyperfine interaction; various models are used for the interaction between the vibrations in the radical and the lattice vibrations. The formulas relate the relaxation time to temperature, magnetic field, and the parameters of the spin hamiltonian.     

Proton field-cycling nuclear magnetic resonance relaxometry in the smectic A mesophase of thermotropic cyanobiphenyls: Effects of sonication

Proton field-cycling nuclear magnetic resonance relaxometry is used to study the spin-lattice relaxation dispersion of selected standard smectic A liquid crystals at different temperatures. Relaxation features at both, in the presence and absence of a monochromatic ultrasonic field are considered. We show that the laboratory-frame spin-lattice relaxation time is mainly governed by translational diffusion. Order director fluctuations (ODF) are less important while rotational diffusion seems to be only relevant near the clearing point. Our study suggests that sonication enhances the ODF contribution in the SmA mesophase. Within the framework of the approach we have outlined, different features associated with the ODF mechanism can be investigated.     

The effect of iodine on the carbon-13 relaxation times of pyridine

The addition of iodine to pyridine not only causes appreciable changes in the ¹³C chemical shifts but also a marked reduction in spin-lattice relaxation times. The effect at the γ-carbon is larger than at the α- and β-carbons. This is consistent with the formation of a pyridine-iodine complex with a preferential tumbling about the C-γ? N? I axis. Elementary theory is applied to approximate the tumbling ratio.     

Effect of water on relaxation processes in biopolymer sorbents

NMR, adsorption, and comparative methods have been employed to study effect of water on relaxation processes in polysaccharides. The development of the segmental mobility of macromolecules upon polysaccharide devitrification, which accompanies the formation of an adsorption layer with a thickness of about two water molecules, has been shown to make the largest contribution to the spin-lattice relaxation processes in the polymer-water system.     

Theoretical aspects of chemically induced magnetic polarization

The role of theory in guiding and simplifying interpretation of electron spin resonance experiments on photochemical and other reactions involving free radical intermediates is surveyed. Emphasis is on models which provide a physical picture as well as quantitative estimates for such phenomena as the radical pair mechanism of chemically induced electron spin polarization (CIDEP), the closely related process of spin exchange during radical-radical encounters, and spin lattice relaxation. Some specific topics discussed are: 1) an improved quantitative model of STo CIDEP combining an initial stage of polarization development followed partial loss of this polarization to spin exchange, 2) the relation between the spin exchange and recombination rate constants, and 3) simplification of spin-lattice relaxation in the common case of spin-rotation relaxation. The modification of the polarization processes in two-dimensional and closed three-dimensional systems is also discussed     

Molecular diffusion on a time scale between nano- and milliseconds probed by field-cycling NMR relaxometry of intermolecular dipolar interactions: application to polymer melts

A formalism is presented permitting the evaluation of the relative mean-squared displacement of molecules from the intermolecular contribution to spin-lattice relaxation dispersion of dipolar coupled spins. The only condition for the applicability is the subdiffusive power law character of the time dependence of the mean-squared displacement as it is typical for the chain mode regime in polymer liquids. Using field-cycling NMR relaxometry, an effective diffusion time range from nano- to almost milliseconds can be probed. The intermolecular spin-lattice relaxation contribution can be determined with the aid of isotopic dilution, that is, mixtures of undeuterated and deuterated molecules. Experiments have been performed with melts of polyethyleneoxide and polybutadiene. The mean-squared segment displacements have been evaluated as a function of time over five decades. The data can be described by a power law. The extrapolation to the much longer time scale of ordinary field-gradient NMR diffusometry gives good coincidence with literature data. The total time range thus covers nine decades.     

Paramagnet enhanced nuclear relaxation of H2 in organic solvents and in H2@C60

We have measured the bimolecular contribution (relaxivity) R1 (M(-1) s(-1)) to the spin-lattice relaxation rate for the protons of H2 and H2@C60 dissolved in organic solvents in the presence of paramagnet nitroxide radicals. It is found that the relaxation effect of the paramagnets is enhanced 5-fold in H2@C60 compared to H2 under the same conditions. 13C relaxivity in C60 induced by nitroxide has also been measured. The resulting value of R1 for 13C is substantially smaller relative to the 1H relaxation in H2@C60 than expected solely on the basis of the smaller magnetic moment of 13C. The observed values of R1 have been analyzed quantitatively using an outer-sphere model for bimolecular spin relaxation to extract an encounter distance, d, as the dependent variable. The resulting values of d for H2 and (13)C60 are similar to the sum of the van der Waals radii for the radical and the corresponding molecule. The value of d for (1)H2@C60 is substantially smaller than the corresponding van der Waals estimates, corresponding to larger than expected values of R1. A possible explanation for the enhanced relaxivity is a contribution from hyperfine coupling. Based on the results reported here, it seems that not only is the hydrogen molecule in H2@C60 not insulated from magnetic contact with the outside world but also the interaction with paramagnets is even stronger than expected based on distance alone.     

高分子链与溶剂分子最短平均距离的~(13)C NMR测定法

<正> 高分子溶液的性质取决于高分子链与溶剂分子的相互作用,由于高分子链与溶剂分子的涨落运动,所以总的结果是整个时间和空间的系综平均。如能得到高分子链与溶剂分子的平均作用距离,那么从理论上就可计算高分子溶液的有关性质,因而具有理论意义。但迄今为止,还未报道测定这种距离的方法。     

Thallium-205 spin lattice relaxation in dialkylthallium(III) derivatives: Importance of chemical shift anisotropy relaxation and effects on NMR spectra of coupled nuclei

A dominant contribution from the chemical shift anisotropy relaxation mechanism to²⁰⁵Tl spin-lattice relaxation in some dialkylthallium(III) derivatives is demonstrated by measurements at two different fields and is also reflected in nmr linewidths of coupled protons, hence suggesting a new and facile method for monitoring changes in²⁰⁵Tl T₁ values.     

Metallic nature and surface diffusion of CO adsorbed on Ru nanoparticles in aqueous media: A 13C NMR study

We report the first observation of the 13C nuclear magnetic resonance spectroscopy (NMR) of 13CO, adsorbed from 13CO saturated 0.5 M sulfuric acid solutions, onto the surfaces of commercial Ru-black nanoparticles. The 13C NMR spectra consist of a symmetrically broadened peak having a large isotropic shift as compared to CO adsorbed onto supported Ru catalysts. The variation of the spin-lattice relaxation rate follows Korringa behavior, indicating the metallic nature of adsorbed CO, in addition to varying across the spectrum in a Korringa-like manner. Motional narrowing of the NMR spectrum at higher temperatures, together with an additional contribution to the spin-lattice relaxation rate, indicate that adsorbed CO undergoes rapid diffusion on the particle surfaces. A two-band model analysis of the NMR results indicates that the CO adsorption bond is weaker on Ru as compared to either Pt or Pd. This is also supported by a reduction in the activation energy for CO diffusion on Ru vs either Pt or Pd nanoparticles.     

Binding Sites,Vibrations and Spin-Lattice Relaxation Times in Europium(II)-Based Metallofullerene Spin Qubits

To design molecular spin qubits with enhanced quantum coherence, a control of the coupling between the local vibrations and the spin states is crucial, which could be realized in principle by engineering molecular structures via coordination chemistry. To this end, understanding the underlying structural factors that govern the spin relaxation is a central topic. Here, we report the investigation of the spin dynamics in a series of chemically designed europium(II)-based endohedral metallofullerenes (EMFs). By introducing a unique structural difference, i. e. metal-cage binding site, while keeping other molecular parameters constant between different complexes, these manifest the key role of the three low-energy metal-displacing vibrations in mediating the spin-lattice relaxation times (T₁). The temperature dependence of T₁ can thus be normalized by the frequencies of these low energy vibrations to show an unprecedentedly universal behavior for EMFs in frozen CS₂ solution. Our theoretical analysis indicates that this structural difference determines not only the vibrational rigidity but also spin-vibration coupling in these EMF-based qubit candidates.     

Evidence for disorder in L-alanine lattice detected by Pulsed-EPR spectroscopy at cryogenic temperatures

The unusual behavior of lattice dynamics of L-alanine has been assigned to intermolecular dynamics and localization of vibrational energy. Recent heat capacity and Pulsed-EPR measurements support presence of thermally activated dynamic orientational disorder in the L-alanine lattice below 20 K. In the present study, the additional evidence for possible thermally activated disordered behavior of L-alanine lattice have been obtained by investigating dependences of longitudinal relaxation time of first stable L-alanine radical, SAR1, on sample cooling rates for the same low temperature interval. The obtained relaxation time by Pulsed-EPR shows clear dependence on cooling rates and this behavior can be explained within two types of suggested spin-lattice relaxation mechanisms for the paramagnetic centers in the hydrogen-bonded organic crystal.     

Vibronic coupling in the ground and excited states of oligoacene cations

The vibrational coupling in the ground and excited states of positively charged naphthalene, anthracene, tetracene, and pentacene molecules is studied on the basis of a joint experimental and theoretical study of ionization spectra using high-resolution gas-phase photoelectron spectroscopy and first-principles correlated quantum-mechanical calculations. Our theoretical and experimental results reveal that, while the main contribution to relaxation energy in the ground state of oligoacene systems comes from high-energy vibrations, the excited-state relaxation energies show a significant redistribution toward lower-frequency vibrations. A direct correlation is found between the nature of the vibronic interaction and the pattern of the electronic state structure.     

Interaction of the human prion PrP(106-126) sequence with copper(II), manganese(II), and zinc(II): NMR and EPR studies

The synthetic peptide encompassing residues 106-126 (PrP106-126, KTNMKHMAGAAAAGAVVGGLG) of the human prion protein was considered for its binding properties toward copper(II), manganese(II) and zinc(II) at pH 5.7. 1H and 13C 1D spectra, 1H spin-lattice relaxation rates, and 1H-15N and 1H-13C HSQC 2D experiments were obtained in the absence and in the presence of metal ions. While Zn(II) was found to yield negligible effects upon any NMR parameter, metal-peptide association was demonstrated by the paramagnetic effects of Cu(II) and Mn(II) upon 1D and 2D spectra. Delineation of structures of metal complexes was sought by interpreting the paramagnetic effect on 1H spin-lattice relaxation rates. Exchange of peptide molecules from the metal coordination sphere was shown to provide sizable contribution to the observed relaxation rates. Such contribution was calculated in the case of Cu(II); whereas the faster paramagnetic rates of peptide molecules bound to Mn(II) were determining spin-lattice relaxation rates almost exclusively dominated by exchange. Proton-metal distances were therefore evaluated in the case of the Cu(II) complex only and used as restraints in molecular dynamics calculations where from the structure of the complex was obtained. The peptide was shown to bind copper through the imidazole nitrogen and the ionized amide nitrogen of His-111 and the amino-terminal group with the terminal carboxyl stabilizing the coordination sphere through ionic interactions. The data were interpreted as to demonstrate that the hydrophobic C-terminal region was not affecting the copper-binding properties of the peptide and that this hydrophobic tail is left free to interact with other target molecules. As for the complex with Mn(II), qualitative information was obtained on carbonyl oxygens of Gly-124 and Leu-125, beyond the terminal Gly-126 carboxyl, being at close distance from the metal ion, that also interacts, most likely, through a hydrogen bond of metal-bound water, with the imidazole ring of His-111.     

The use of 1H and 13C spin-lattice relaxation rates in the structure determination of adducts of adamantane-1-carbonitrile and lanthanide chelates in solution; comparison with the results of measurements of lanthanide induced shifts

Gd(fod)₃ induced enhancements of ¹H and ¹³ spin-lattice relaxation rates showed the Gd-N distance in adducts of Gd(fod)₃ and adamantane-1-carbonitrile to be 2.60 Å. A good estimate of the intermolecular contribution to the enhancement of the relaxation appears to be essential in this method of structural analysis. The results of this investigation are compared with those of calculations based on lanthanide induced shifts.     

Entanglements and elasticity in polybutadiene networks

Polybutadiene networks were prepared by peroxide crosslinking of monodisperse 1,4-polybutadienes both in solution and in bulk. The effect of the entangled sol fraction on the elastic modulus of high-molecular-weight polybutadiene was observed in stress relaxation measurements. Sol fraction was shown to make a large contribution to the Mooney–Rivlin 2C₂ term. This effect was also observed on the molecular level in NMR spin-spin relaxation measurements. For networks crosslinked in bulk the stress relaxation measurements suggest the presence of trapped entanglements. The 2C₂ term is insensitive to sol extraction in these networks. NMR spin-lattice relaxation measurements in the rotating frame at 4.68 kHz verify the presence of additional effective crosslinks in these networks.