Regulation of thermodynamics and kinetics of silica nucleation during the silicification process in higher plants

The formation mechanism of SiO₂ aggregates is controversial because two contrasting hypotheses are often proposed to explain plant silicification. In this review, we summarize the physicochemical fundamentals of amorphous silica nucleation and discuss how plants regulate the process of silicification by influencing the thermodynamics and kinetics of silica nucleation. At silicification positions, plants overcome the thermodynamic barrier by establishing the supersaturation of the H₄SiO₄ solution and reducing the interfacial free energy. Among the thermodynamic-drivers, the establishment of supersaturation of H₄SiO₄ solution mainly depends on the expression of Si transporters for H₄SiO₄ supply, evapotranspiration for concentrating Si, and the other solutes in H₄SiO₄ solution for influencing the dissolution equilibrium of SiO₂; while the interfacial free energy was reduced seemingly by the overexpression Na⁺/H⁺ antiporter SOS1 in high NaCl-stressed rice. Moreover, some kinetic-drivers, such as silicification-related proteins (Slp1 and PRP1) and new cell wall components, are actively expressed or synthesized by plants to interact with silicic acid, thereby reducing the kinetic barrier. According to classical nucleation theory, when the thermodynamic barrier is overcome, the super-saturated silicic acid solution (such as H₄SiO₄ in xylem sap) does not necessarily have to precipitate, just has the potential ability to precipitation. Thus, based on the mediators of SiO₂ deposition at the thermodynamic-driven stage, it is difficult to evaluate whether the process of plant silicification is active or passive. We conclude that the characteristics of kinetic-drivers determine the mechanism of plant silicification.