Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds:A Step toward Nacre Mimicry

The production of novel composite materials, assembled using biomimetic polymers known as peptoids (N-substituted glycines) to nucleate CaCO3, can open new pathways for advanced material design. However, a better understanding of the heterogeneous CaCO3 nucleation process is a necessary first step. We determined the thermodynamic and kinetic parameters for calcite nucleation on self-assembled monolayers (SAMs) of nanosheet-forming peptoid polymers and simpler, alkanethiol analogues. We used nucleation rate studies to determine the net interfacial free energy (γ net) for the peptoid-calcite interface and for SAMs terminated with carboxyl headgroups, amine headgroups, or a mix of the two. We compared the results with γ net determined from dynamic force spectroscopy (DFS) and from density functional theory (DFT), using COSMO-RS simulations. Calcite nucleation has a lower thermodynamic barrier on the peptoid surface than on carboxyl and amine SAMs. From the relationship between nucleation rate (J 0) and saturation state, we found that under low-saturation conditions, i.e. <3.3 (pH 9.0), nucleation on the peptoid substrate was faster than that on all of the model surfaces, indicating a thermodynamic drive toward heterogeneous nucleation. When they are taken together, our results indicate that nanosheet-forming peptoid monolayers can serve as an organic template for CaCO3 polymorph growth

A mycorrhizal fungus grows on biochar and captures phosphorus from its surfaces

Biochar application to soils has potential to simultaneously improve soil fertility and store carbon to aid climate change mitigation. While many studies have shown positive effects on plant yields, much less is known about the synergies between biochar and plant growth promoting microbes, such as mycorrhizal fungi. We present the first evidence that arbuscular mycorrhizal (AM) fungi can use biochar as a physical growth matrix and nutrient source. We used monoxenic cultures of the AM fungus Rhizophagus irregularis in symbiosis with carrot roots. Using scanning electron microscopy we observed that AM fungal hyphae grow on and into two contrasting types of biochar particles, strongly attaching to inner and outer surfaces. Loading a nutrient-poor biochar surface with nutrients stimulated hyphal colonization. We labeled biochar surfaces with P-33 radiotracer and found that hyphal contact to the biochar surfaces permitted uptake of P-33 and its subsequent translocation to the associated host roots. Direct access of fungal hyphae to biochar surfaces resulted in six times more P-33 translocation to the host roots than in systems where a mesh prevented hyphal contact with the biochar. We conclude that AM fungal hyphae access microsites within biochar, that are too small for most plant roots to enter (<10 mu m), and can hence mediate plant phosphorus uptake from the biochar. Thus, combined management of biochar and AM fungi could contribute to sustainable soil and climate management by providing both a carbon-stable nutrient reservoir and a symbiont that facilitates nutrient uptake from it. (C) 2014 Elsevier Ltd. All rights reserved