Shaping Magnetite with Poly-l-arginine and pH: From Small Single Crystals to Large Mesocrystals.

Control over particle size, size distribution, and colloidal stability are central aims in producing functional nanomaterials. Recently, biomimetic approaches have been successfully used to enhance control over properties in the synthesis of those materials. Magnetotactic bacteria produce protein-stabilized magnetite away from its thermodynamic equilibrium structure. Mimicking the bacteria's proteins using poly-l-arginine we show that by simply increasing the pH, the dimensions of magnetite increase and a single- to mesocrystal transformation is induced. Using synchrotron X-ray diffraction and transmission electron microscopy, we show that magnetite nanoparticles with narrow size distributions and average diameters of 10 ± 2 nm for pH 9, 20 ± 2 nm for pH 10, and up to 40 ± 4 nm for pH 11 can be synthesized. We thus selectively produce superparamagnetic and stable single-domain particles merely by controlling the pH. Remarkably, while an increase in pH brings about a thermodynamically driven decrease in size for magnetite without additives, this dependency on pH is inverted when poly-l-arginine is present.