The short-time expansion of the diffusion coefficient in powers of t1/2 is universally connected to structural parameters of the boundaries restricting the diffusive motion. The t1/2-term is proportional to the surface-to-volume ratio. The t-term is related to permeability and curvature. The short-time expansion can be measured by application of oscillating gradients of long total duration. For oscillating gradients, the inverse of the oscillation frequency becomes the relevant time scale. The purpose of this work is to show that the oscillating gradient approach is blind to the t-term. Thus, the t-term does not bias the determination of the t1/2-term in experiments.
The short-time expansion of the diffusion coefficient in powers of $$$t^{1/2}$$$, where $$$t$$$ is the diffusion time, is universally connected to structural parameters of the boundaries restricting the diffusive motion1. The $$$t^{1/2}$$$-term is proportional to the surface to volume ratio. The $$$t$$$-term is related to permeability and curvature. The short-time expansion can be measured by the use of diffusion encodings of short total duration or by application of oscillating gradients of long total duration2. For oscillating gradients, the inverse of the oscillation frequency becomes the relevant time scale. The purpose of this work is to show that the oscillating gradient approach is blind to the $$$t$$$-term.
The effective diffusion coefficient in the short-time limit is
$$D(t)=\frac{<(x(t)-x(0))^2>}{2t}=\frac{<x(t)^2+x(0)^2-2x(t)x(0)>}{2t}=∑_{n=0}M_nc_nt^{n/2}$$with the $$$t^0$$$-term $$M_0=D_0,$$ the $$$t^{1/2}$$$-term$$M_1=-\frac{4}{3d\sqrt{π}}\frac{S}{V}\sqrt{D_0},$$and the $$$t$$$-term$$M_2=\frac{S}{V}(\frac{1}{d}\kappa-\frac{1}{12}D_0\overline{R^{-1}}).$$Here, $$$D_0$$$ is the free diffusion coefficient, $$$S/V$$$ is the surface-to-volume ratio, $$$d$$$ is the dimension, $$$\kappa$$$ is the membrane permeability, and $$$\overline{R^{-1}}$$$ is a term related to the membrane curvature. In diffusion MR experiments, $$$<x(t)^2>$$$ and $$$<x(0)^2>$$$ do not contribute to the signal attenuation due to the rephasing condition. Hence the diffusion spectrum $$$\mathcal{D}(\omega)$$$ may be written as$$\frac{\mathcal{D}(\omega)}{\omega^2}=\frac{1}{2}\int_{-\infty}^\infty⟨x(t_2 )x(t_1 )⟩ e^{-i\omega t_{21}} dt_{21}=-\frac{1}{2}\sum_{n=0}\int_{-\infty}^\infty M_n |t_{21}|^{1+n/2}e^{-i\omega t_{21}}dt_{21}.$$with $$$t_{21}=t_2-t_1$$$. The last term is a Fourier transform: $$\frac{1}{2}\int_{-\infty}^\infty |t_{21}|^{1+n/2}e^{-i\omega t_{21}}dt_{21}=-\omega^{-2-n/2} cos(n\pi/4)\Gamma(2+n/2)$$ for $$$\omega>0$$$ and $$$n≥0$$$. Hence one finds:$$\mathcal{D}(\omega)=M_0+M_1 \sqrt{\frac{π}{2}}\frac{3}{4\omega^{1⁄2}}+0\cdot M_2+O(\omega^{-3⁄2} )$$and$$\mathcal{D}_{app}(\tau):=\mathcal{D}(2\pi/\tau)=D_0+M_1\frac{3}{8}\tau^{1⁄2}+0\cdot M_2+O(\tau^{3⁄2}).$$ Thus the $$$t$$$-term is not visible in oscillating gradient diffusion MR diffusion experiments, which build on the experimental detection of $$$D(\omega)$$$. Note that the value of coefficient accompanying the $$$t^{1/2}$$$-term was reported previously (e.g. in 3).
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