Crystallization is inherently an interfacial phenomenon that can be mediated through the use of additives, termed modifiers, which adsorb at specific crystal surfaces and influence the anisotropic rates of crystal growth. In pathological biomineralization, the formation of minerals is believed to be regulated in vivo by the interaction of urinary constituents with crystal interfaces. Here we examine the role of native growth modifiers of calcium oxalate monohydrate (COM), which is the most prevalent crystalline constituent of human kidney stones, and serves as a model for examining modifier-crystal molecular recognition [1]. Many species, such as proteins and trace metals, are putative growth modifiers that display an affinity for binding to specific surfaces of COM crystals to suppress (or in some cases promote [2]) crystal growth. Our studies have revealed interesting trends among modifiers with varying charge density and hydrogen-bonding moieties that suggest the diffuse double layer surrounding COM crystal surfaces plays a significant role in modifier-crystal interactions. In this talk we will discuss the effects of alkali metals and alkaline earth metals on COM crystallization. To this end, we employ a combination of bulk crystallization assays and interfacial studies. To obtain better understanding of the interfacial phenomena during COM surface growth in the presence of modifiers, we have employed atomic force microscopy (AFM) to observe in situ the dynamics of layer-by-layer surface growth and the mechanisms of modifier inhibition. We couple these studies with bulk assays to assess the influence of growth modifiers on the crystal size and habit. Collectively, these studies are a basis for ongoing initiatives to design novel drug candidates for pathological diseases [3] and a generalized platform for the rational design of inorganic and advanced materials with tailored properties. [1] Farmanesh, S., Ramamoorthy, S., Chung, J., Asplin, J.R., Karande, P., Rimer, J.D., J. Am. Chem. Soc. 136 (2014) 367-376 [2] Farmanesh, S., Chung, J., Kwak, J.H., Sosa, R.D., Karande, P., Rimer, J.D., J. Am. Chem. Soc. 136 (2014) 12648-12657 [3] Rimer, J.D., An, Z., Zhu, Z., Lee, M.H., Goldfarb, D.S., Wesson, J.A., Ward, M.D., Science 330 (2010) 337-341

Ionic and molecular modifiers of calcium oxalate crystallization: Tailoring interfacial interactions

249th National Meeting (2015)

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