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  1. Abstract Nutrient foraging by fungi weathers rocks by mechanical and biochemical processes. Distinguishing fungal-driven transformation from abiotic mechanisms in soil remains a challenge due to complexities within natural field environments. We examined the role of fungal hyphae in the incipient weathering of granulated basalt from a three-year field experiment in a mixed hardwood-pine forest (S. Carolina) to identify alteration at the nanometer to micron scales based on microscopy-tomography analyses. Investigations of fungal-grain contacts revealed (i) a hypha-biofilm-basaltic glass interface coinciding with titanomagnetite inclusions exposed on the grain surface and embedded in the glass matrix and (ii) native dendritic and subhedral titanomagnetite inclusions in the upper 1–2 µm of the grain surface that spanned the length of the fungal-grain interface. We provide evidence of submicron basaltic glass dissolution occurring at a fungal-grain contact in a soil field setting. An example of how fungal-mediated weathering can be distinguished from abiotic mechanisms in the field was demonstrated by observing hyphal selective occupation and hydrolysis of glass-titanomagnetite surfaces. We hypothesize that the fungi were drawn to basaltic glass-titanomagnetite boundaries given that titanomagnetite exposed on or very near grain surfaces represents a source of iron to microbes. Furthermore, glass is energetically favorable to weathering in the presencemore »of titanomagnetite. Our observations demonstrate that fungi interact with and transform basaltic substrates over a three-year time scale in field environments, which is central to understanding the rates and pathways of biogeochemical reactions related to nuclear waste disposal, geologic carbon storage, nutrient cycling, cultural artifact preservation, and soil-formation processes.« less
    Free, publicly-accessible full text available December 1, 2023
  2. Understanding how to control the nucleation and growth rates is crucial for designing nanoparticles with specific sizes and shapes. In this study, we show that the nucleation and growth rates are correlated with the thermodynamics of metal–ligand/solvent binding for the pre-reduction complex and the surface of the nanoparticle, respectively. To obtain these correlations, we measured the nucleation and growth rates by in situ small angle X-ray scattering during the synthesis of colloidal Pd nanoparticles in the presence of trioctylphosphine in solvents of varying coordinating ability. The results show that the nucleation rate decreased, while the growth rate increased in the following order, toluene, piperidine, 3,4-lutidine and pyridine, leading to a large increase in the final nanoparticle size (from 1.4 nm in toluene to 5.0 nm in pyridine). Using density functional theory (DFT), complemented by 31 P nuclear magnetic resonance and X-ray absorption spectroscopy, we calculated the reduction Gibbs free energies of the solvent-dependent dominant pre-reduction complex and the solvent-nanoparticle binding energy. The results indicate that lower nucleation rates originate from solvent coordination which stabilizes the pre-reduction complex and increases its reduction free energy. At the same time, DFT calculations suggest that the solvent coordination affects the effective capping of themore »surface where stronger binding solvents slow the nanoparticle growth by lowering the number of active sites (not already bound by trioctylphosphine). The findings represent a promising advancement towards understanding the microscopic connection between the metal–ligand thermodynamic interactions and the kinetics of nucleation and growth to control the size of colloidal metal nanoparticles.« less
  3. Controlling the size distribution of nanoparticles is important for many applications and typically involves the use of ligands during synthesis. In this study, we show that the mechanism of size focusing involves a dependence of the growth rate on the size of the nanoparticles and the ligand coverage on the surface of the nanoparticles. To demonstrate these effects, we used in situ small angle X-ray scattering (SAXS) and population balance kinetic modeling (PBM) to investigate the evolution of size distribution during the synthesis of colloidal Pd metal nanoparticles. Despite temporal overlap of nucleation and growth, our in situ SAXS show size focusing of the distribution under different synthetic conditions (different concentrations of metal and ligand as well as solvent type). To understand the mechanism of size focusing using PBM, we systematically studied how the evolution of the nanoparticle size distribution is affected by nucleation rate, and dependence of the growth rate constant on ligand surface coverage, and size of the nanoparticles. We show that continuous nucleation contributes to size defocusing. However, continuous nucleation results in different reaction times for the nanoparticle population leading to time and size-dependent ligand surface coverage. Using density functional theory (DFT) calculations and Brønsted–Evans–Polanyi relations, wemore »show that as the population grows, larger nanoparticles grow more slowly than smaller ones due to lower intrinsic activity and higher ligand coverage on the surface. Therefore, despite continuous nucleation, the faster growth of smaller nanoparticles in the population leads to size focusing. The size focusing behaviour (due to faster growth of smaller nanoparticles) was found to be model independent and similar results were demonstrated under different nucleation and growth pathways ( e.g. growth via ion reduction on the surface and/or monomer addition). Our results provide a microscopic connection between kinetics and thermodynamics of nanoparticle growth and metal–ligand binding, and their effect on the size distribution of colloidal nanoparticles.« less