The colloidal nature of asphaltenes impacts various physical properties of crude oils and exhibits a series of aggregation phenomena. Optical diffusion experiments at very low concentrations have measured the size of asphaltene monomers; ultrasound experiments have observed a nanoaggregation transition in toluene. In this work, we use a suite of nuclear magnetic resonance (NMR) methods to study the molecular dynamics and thermodynamics of aggregation in dilute asphaltene solutions. The molecular size of the single asphaltenes and aggregates is determined from NMR diffusion measurements. We observe an abrupt drop of the asphaltene diffusion constant at the onset of aggregation. We also measured the hydrogen index and observed a reduction in the spin-echo signal because of restricted motion of the alkyl chains upon aggregation. The enthalpy of aggregation is found to be negative, most likely because of π-stacking interactions. The entropy of aggregation is found to be positive, which is unexpected for a nonpolar solution. We also discuss the interpretation of these results.

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We show experimentally and theoretically that two readily observed effects in solution nuclear magnetic resonance (NMR)-radiation damping and the dipolar field-combine to generate bizarre spin dynamics (including chaotic evolution) even with extraordinarily simple sequences. For example, seemingly insignificant residual magnetization after a crusher gradient triggers exponential regrowth of the magnetization, followed by aperiodic turbulent spin motion. The estimated Lyapunov exponent suggests the onset of spatial-temporal chaos and the existence of chaotic attractors. This effect leads to highly irreproducible experimental decays that amplify minor nonuniformities such as temperature gradients. Imaging applications and consequences for other NMR studies are discussed.

Artifacts arising from aperiodic turbulent spin dynamics in gradient-based nuclear magnetic resonance (NMR) applications are comprehensively surveyed and numerically simulated by a nonlinear Bloch equation. The unexpected dynamics, triggered by the joint action of radiation damping and the distant dipolar field, markedly deteriorate the performance of certain pulse sequences incorporating weak pulsed-field gradients and long evolution times. The effects are demonstrated in three general classes of gradient NMR applications: solvent signal suppression, diffusion measurements, and coherence pathway selection. Gradient-modulated solvent transverse magnetization can be partially rephased in a series of self-refocusing gradient echoes that blank out solute resonances in the CHESS (chemical-shift-selective spectroscopy) and WATERGATE (gradient-tailored water suppression) solvent suppression schemes. In addition, the discovered dynamics contribute to erratic echo attenuation in pulsed gradient spin echo (PGSE) and PGSE stimulated echo diffusion measurements and produce coherence leakage in gradient-selected DQFCOSY and HMQC experiments. Specific remedies for minimizing unwanted effects are presented.

The eigenmodes of spin diffusion provide a mathematical solution to the diffusion equation and the eigenmode spectrum can be used to characterize the internal space of porous media. The dynamics of these eigenmodes is affected by the presence of an inhomogeneous magnetic field inside the pores. In this paper we examine the behavior of the diffusion eigenmodes as a function of the spatially dependent encoding phase due to the inhomogeneous internal field. We show that in the limit of weak phase encoding, the first diffusion modes are predominantly excited. In this regime the excited signal is found to be linearly proportional to the encoding phase and the eigenmode spectrum reflects the pore size distribution. When the encoding phase is larger than 2π, the spectrum can be dominated by the higher eigenmodes.