PVP-coated Gd-grafted nanodiamonds as a novel and potentially safer contrast agent for in vivo MRI.

Purpose: Testing the potential use of saline suspension of polyvinylpyrrolidone (PVP)-coated gadolinium(Gd)-grafted detonation nanodiamonds (DND) as a novel contrast agent in MRI.

Methods: Stable saline suspensions of highly purified de-agglomerated Gd-grafted DND particles coated by a PVP protective shell were prepared. T and T proton relaxivities of the suspensions with varying gadolinium concentration were measured at 8 Tesla.

Dipolar nuclear polarization via the spin diffusion of a dipole order.

We propose transfer of the paramagnetic impurity (PI) polarization to nuclei in bulk, outside the diffusion barrier, by using dipolar system of the nuclear spins. The transfer can overcome influence of the diffusion barrier and is proposed to be implemented in four stages. At the first stage, transition of the Zeeman PI order to the Zeeman order of nuclear spins inside the spin-diffusion barrier is occurred.

Examining relaxivities in suspensions of nanodiamonds grafted by magnetic entities: comparison of two approaches.

Objectives: Detonation nanodiamonds (DND) with Gd ions directly grafted to the DND surface have recently demonstrated enhanced relaxivity for protons in aqueous suspensions. Herewith, the relaxivity measurements were done on a series of suspensions with the gadolinium content varied by changing number of Gd ions grafted per each DND particle whereas the DND content in each suspension was kept the same. Such an approach to vary the contrast agent content differs from that commonly used in the relaxivity measurements.

Location of paramagnetic defects in detonation nanodiamond from proton spin-lattice relaxation data.

We developed an approach for determining location of intrinsic paramagnetic defects in nanodiamonds from the data of proton spin-lattice relaxation of the surface hydrogen atoms. The approach was applied to the detonation nanodiamond (DND) of the diameter of 5 nm. We found that dangling bonds with unpaired electron spins are located within the near-surface belt at the distance of 0.

Anisotropy of spin-spin and spin-lattice relaxation times in liquids entrapped in nanocavities: Application to MRI study of biological systems.

Spin-spin and spin-lattice relaxations in liquid or gas entrapped in nanosized ellipsoidal cavities with different orientation ordering are theoretically investigated. The model is flexible in order to be applied to explain experimental results in cavities with various forms, from very prolate up to oblate ones, and different degree of ordering of nanocavities. In the framework of the considered model, the dipole-dipole interaction is determined by a single coupling constant, which depends on the form, size, and orientation of the cavity and number of nuclear spins in the cavity.

Nuclear spin-lattice relaxation in nanofluids with paramagnetic impurities.

We study the spin-lattice relaxation of the nuclear spins in a liquid or a gas entrapped in nanosized ellipsoidal cavities with paramagnetic impurities. Two cases are considered where the major axes of cavities are in orientational order and isotropically disordered. The evolution equation and analytical expression for spin lattice relaxation time are obtained which give the dependence of the relaxation time on the structural parameters of a nanocavity and the characteristics of a gas or a liquid confined in nanocavities.

Size dependence of 13C nuclear spin-lattice relaxation in micro- and nanodiamonds.

Size dependence of physical properties of nanodiamond particles is of crucial importance for various applications in which defect density and location as well as relaxation processes play a significant role. In this work, the impact of defects induced by milling of micron-sized synthetic diamonds was studied by magnetic resonance techniques as a function of the particle size. EPR and (13)C NMR studies of highly purified commercial synthetic micro- and nanodiamonds were done for various fractions separated by sizes.

(13)C spin-lattice relaxation in nanodiamonds in static and magic angle spinning regimes.

We report on (13)C nuclear spin-lattice relaxation time (T1) dependence on the magic-angle-spinning (MAS) rate in powder nanodiamond samples. We confirm that the relaxation is caused by interaction of nuclear spins with fluctuating electron spins of localized paramagnetic defects. It was found that T1 is practically not affected by MAS for small particles, while for larger particles with lower defect density T1 is different in static and MAS regimes and reveals elongation with increasing MAS rate.

MQ NMR dynamics in dipolar ordered state at negative temperature.

We investigate theoretically the Multiple Quantum (MQ) NMR dynamics at negative absolute temperatures in systems of nuclear spins 1/2 coupled by the dipole-dipole interactions and with the initial conditions determined by the dipolar ordered state. Two different methods of MQ NMR are used. One of them is based on the measurement of the dipolar energy.

Antiferromagnetic Ordering of Magnetic Clusters Units in Nb(6)F(15).

We have studied the magnetic cluster compound Nb(6)F(15) which has an odd number of 15 valence electrons per (Nb(6)F(12))(3+) cluster core, as a function of temperature using nuclear magnetic resonance, magnetic susceptibility, electron magnetic resonance and neutron powder diffraction. Nuclear magnetic resonance of the (19)F nuclei shows two lines corresponding to the apical F(a-a) nucleus, and to the inner F(i) nuclei. The temperature dependence of the signal from the F(i) nuclei reveals an antiferromagnetic ordering at T < 5 K, with a hyperfine field of ~2 mT.

Spin diffusion in multiple pulse spin-locking in solids containing paramagnetic impurities.

Spin diffusion and spin-lattice relaxation in solids containing paramagnetic impurities under influence of a multiple-pulse spin-locking radio-frequency sequence are studied theoretically and experimentally. The diffusion equation obtained provides a clue for determination of the time dependent magnetization. The spin-lattice relaxation time is calculated as a function of the correlation time and multiple-pulse field parameters.

Dynamics of multiple quantum coherences in dipole-coupling spins in solid.

A perturbation method deals with dipolar coupling spins in solids is presented. As example of application the method, the multiple-quantum coherence dynamics in clusters of a linear chain of four nuclear spins and a ring of six spins coupled by dipole-dipole interaction are considered. The calculated 0Q and 2Q intensities in a linear chain of four nuclear spins and 6Q intensity in a ring of six spins vs.

Spin diffusion of dipolar energy in NQR.

The theory of spin diffusion was extended to the case of nuclear dipolar order in solids containing paramagnetic impurities and nuclei with spin I > 1/2 having nuclear quadrupole moment. We show that spin diffusion process of dipolar order takes place in solids containing paramagnetic impurities. At the start of relaxation process, the direct relaxation regime is realized with non-exponential time dependence.

Spin diffusion and nuclear spin-lattice relaxation in irradiated solids: a multiple-pulse NQR study.

We present a detailed theoretical and experimental NQR multiple-pulse spin-locking study of spin-lattice relaxation and spin diffusion processes in the presence of paramagnetic impurities in solids. The relaxation function of the nuclear spin system at the beginning of the relaxation process is given by exp (-t/T1rho)alpha, where T1rho is spin-lattice relaxation time in rotating frame and alpha = d/6, d is the sample dimensionality. Then the relaxation proceeds asymptotically to an exponential function of time, which was attributed to the spin-diffusion regime.

Spin-locking in one pulse NMR experiment.

The response of a spin system to a long (in comparison to spin-spin relaxation time T2) radiofrequency pulse has been studied. We observed that the magnetization after the long pulse does not fall to zero at time t >> T2 for both on-resonance and off-resonance conditions. The dependencies of the magnetization on frequency offset, linewidth and radiofrequency power are investigated, both theoretically and experimentally.

Fractional power time dependence of the nuclear magnetization in the presence of paramagnetic impurities.

We extend the theory of growth of the nuclear magnetization in the presence of paramagnetic impurities and the absence of spin diffusion to the case of multi-paramagnetic centers. We show that for short times after saturation pulses, the rate of growth of the magnetization is proportional to t alpha where t is the time and alpha = 1/3, 1/2 and 2/3 for one-, two- and three-dimensional systems, respectively. We also present experimental data for which the total time-dependent magnetization is proportional to exp[-(t/T1) alpha], which reduces to the above time dependence for short times.

Non-exponential behavior of the nuclear magnetization in H-doped copper oxides.

Measurement of the spin lattice relaxation time in H-doped Y2BaCuO5 and YBa2Cu3O6 has revealed a power law growth of the nuclear magnetization M for short times following a saturation pulse sequence. Preliminary experimental results yield exponents of 1/2 and 1/3, depending on the amount of hydrogen present in the sample. We extend Blumberg's theory for relaxation due to paramagnetic centers via dipole-dipole interaction in the absence of spin diffusion to obtain M approximately tD/6 where D is the dimensionality of the system.