Three-dimensional Periodic and Fractal Precipitation in Metal Ion−Deoxycholate System:  A Model for Gallstone Formation

Abstract

It was recently suggested that the periodic and fractal precipitation of calcium salts and proteins in cholesterol gallstonesis closely related to the process of stone formation. The present study is to mimic the process of gallstone growth in vitro. We demonstrate for the first time that a three-dimensional structure of periodic rings (Liesegang ring) and/or fractal patterns can be produced by metal ion and deoxycholate precipitation, which are similar to gallstones. Precipitation in a periodic pattern occurs more often than in a fractal structure. Using X-ray diffraction, polarized light microscope, Fourier transform-infrared (FT-IR), and extended X-ray absorption fine structure (EXAFS), we studied the pattern formation mechanisms of both types of structures. The results indicate that the rate of nucleation in the crystal growth is a crucial element to affect the pattern formation. The pattern selection between periodic and fractal type depends on the crystal growth speed and the rate of nucleation.

Patterns with High Rhythmicity Levels in Multicomponent Liesegang Systems

“…Studies on two-salt Liesegang systems yielded interesting band alternations or overlaps, [23,31] or even a mixture of banded and fractal precipitate structures. [6] Similarities with our observed rhythmicities are scarcely observed in natural systems or conjectured using nonlinear dynamical models. Although the latter could involve widely different mechanisms, the connection between laboratory observations and other nonlinear dynamical systems that exhibit a similar behavior provides a clear stimulus for research to unravel the complexity of the dynamics.…”

“…Rhythmic patterns are manifest in bacteria; [2,3] cellular, nerve, and cardiac systems; [4,5] gallstones, [6] agates and rocks, [7][8][9][10][11] and many other systems, on a huge range of timescales. In some instances, periodic behavior can evolve into complex rhythmicity levels, or break down into a chaotic regime, as some parameters cross a critical value.…”

Inorganic hierarchical nanostructures induced by concentration difference and gradient

“…Our diffusion-controlled crystallization process is somewhat similar to diffusion-limited aggregation (DLA) processes, which are commonly seen in the formation of fractal patterns under farfrom-equilibrium conditions [48]. Since the 1980s, considerable attention has been paid to DLA mainly due to its importance in the morphological evolution of minerals in biological systems and biomimetic processes [49]. However, single crystals with strong anisotropy and low disorder like the hierarchical nanocrystals we prepared here have seldom been obtained via DLA processes [50].…”

Characteristically shaped ZnO particles produced by periodic precipitation in organic gel media

“…In particular, a layered architecture produced in gel by the periodic precipitation of inorganic salts, such as PbI 2 , AgI, or PbCl 2 , is known as Liesegang rings [17]. The layered structures are interesting with regard to natural periodic phenomena in geological and biological minerals [21,22] and modern thermodynamics [23]. However, the fascinating phenomena have not been applied to practical materials barring exception of the banded structure of calcium phosphate [24,25], CuO [26,27], and the Cd-Sn alloy [28].…”