Higher-Order Organization by Mesoscale Self-Assembly and Transformation of Hybrid Nanostructures Helmut Cölfen and Stephen Mann* Keywords: biomineralization · crystal growth · materials science · self assembly · solid state chemistry 2350 The organization of nanostructures across extended length scales is a From the Contents key challenge in the design of integrated materials with advanced 2351 functions. Current approaches tend to be based on physical methods, 1. Introduction such as patterning, rather than the spontaneous chemical assembly and 2. Kinetic Control of Nucleation transformation of building blocks across multiple length scales. It and Growth 2352 should be possible to develop a chemistry of organized matter based on emergent processes in which time- and scale-dependent coupling of 3. Aggregation-Mediated 2353 interactive components generate higher-order architectures with Pathways of Crystal Growth embedded structure. Herein we highlight how the interplay between 4. Mesoscale Self-Assembly of aggregation and crystallization can give rise to mesoscale self- Nanoparticle Arrays 2356 assembly and cooperative transformation and reorganization of hybrid inorganic–organic building blocks to produce single-crystal 5. Mesoscale Transformations and Emergent Nanostructures 2357 mosaics, nanoparticle arrays, and emergent nanostructures with complex form and hierarchy. We propose that similar mesoscale 6. Mesoscale Transformations and processes are also relevant to models of matrix-mediated nucleation in Matrix-Mediated Nucleation in biomineralization. Biomineralization 2361 7. Summary and Outlook 2362 1. Introduction It is self evident that the organization and transformation On the other hand, it should be possible to develop a of matter and energy are fundamental aspects of the universe. chemistry of organized matter that couples together synthesis How these processes occur and the nature of the properties and self assembly to produce, in situ, complex higher order they encode are quintessential questions for all scientific structures. In such cases, the embedding of structures over disciplines past and present. In this regard, chemistry occupies multiple length scales will arise as an emergent property that the middle ground between physics and biology as it deals is not directly related to the smallest building blocks but is with the ordering and rearrangement of atoms at the dependent on how these units evolve in time and space. Thus, molecular level, rather than the fundamental subatomic different driving forces will operate at various stages along the nature of matter or its animation in macroscopic time synthesis construction pathway such that these forces dependent structures. Nanochemistry aims to extend the become superimposed mechanistically. For example, whereas traditional length scales of synthetic chemistry and exploit the localized molecular interactions can dominate ordering collective properties of organized assemblies produced by transitions on the nanoscale, surface forces are important in processes, such as, controlled crystallization and supramolec determining how nanostructures become assembled at the ular complementarity. Although many approaches seek to mesoscopic level. And beyond the colloidal regime, mechan mimic the information processing and sensing capabilities of ical forces, such as internal strain, can drive transformations biological nanostructures, they often lack the inherent that result in macroscopic order. materials building properties typical of organisms, which are It seems unlikely that significant levels of complexity can essential if nanostructures are to be organized across many emerge for single component systems as the scope for switch length scales and used as functional materials within inte ing between these different length scale dependent regimes is grated systems. For this reason, strategies have been devel severely limited by homogeneity. But increasing the number oped for the long range organization and assembly of nano of interactive components should significantly enhance the structured phases. For example, chemical and microfabrica diversity of emergent structures, particularly when inorganic tion methods can be combined to produce externally pat and organic building blocks are present because of the terned materials,[1, 2] whereas spontaneous processes associ ated with solvent evaporation,[3,4] molecular cross linking,[5,6] or programmed recognition[7 9] have been used to control the [*] Prof. S. Mann deposition of nanoparticle based superlattices. Although School of Chemistry promising, these approaches have disadvantages associated University of Bristol with the sequential processing and the physical fabrication, as Bristol BS8 1TS (UK) Fax: (+44)117 929 0509 well as limitations arising from the restricted number of E mail: [email protected] superlattices available because of thermodynamic (packing) Dr. H. Cölfen constraints on self assembly. Indeed, structural organization Max Planck Institut für Kolloid und Grenzflächenforschung, Kol in many of these systems depends on physics and crystal loidchemie engineering rather than chemistry. Forschungscampus Golm, 14424 Potsdam (Germany) 2351 Mg2+ ions required result in the kinetic precipitation of aragonite. Kinetic control of crystallization can be achieved by modifying the interactions of nuclei and developing crystals with solid surfaces and soluble molecules.[28] Such processes influence the structure and composition of the nuclei, particle size, texture, habit and aggregation, and stability of inter mediate phases. In biomineralization, for example, structured organic surfaces are considered to play a key role in organic matrix mediated deposition by lowering the activation energy of nucleation of specific crystal faces and polymorphs through interfacial recognition (see Section 6 for further details).[29] Soluble macromolecules and organic anions, as well as 2+ 3À inorganic ions, such as Mg and PO4 , can also have a marked kinetic effect on crystallization, particularly with regard to polymorph selectivity and habit modification. These Figure 1. Crystallization pathways under thermodynamic and kinetic control. Whether a system follows a one step route to the final mineral interactions can be highly specific; for example, proteins phase (pathway A) or proceeds by sequential precipitation (pathway B), extracted either from calcite or aragonite containing layers of depends on the free energy of activation (DG) associated with nuclea the abalone shell induce the crystallization of calcite or tion (n), growth (g), and phase transformation (t). Amorphous phases aragonite, respectively, when added to supersaturated sol are common under kinetic conditions. utions of calcium hydrogen carbonate in the laboratory.[30] Atomic force microscope (AFM) studies[31] indicate that the macromolecules bind to growth sites on well defined crystal readily described by the classical model of nucleation, which surfaces and influence the kinetics of crystal growth from is based on a thermodynamic treatment of the interplay solution in accordance with the classical model of secondary between energy gain through bulk crystallization and energy nucleation.[32] Although there is much experimental evidence loss through increase in surface area.[17] to support these molecular based mechanisms, the studies Kinetically driven crystallization often involves an initial usually concern macroscopic crystals with well established amorphous phase that may be nonstoichiometric, hydrated, faces and edges, so information about the early stages of and susceptible to rapid phase transformation. Amorphous growth at the colloidal level are not generally available. calcium carbonate (ACC) for instance is highly soluble and Significantly, as discussed in Section 3, recent studies indicate rapidly transforms to calcite, vaterite, or aragonite unless that aggregation of primary particles can be an important kinetically stabilized. In biomineralization, this stabilization is mechanism of crystallization at the mesoscopic length scale, 2+ 3À achieved by ions such as Mg and PO4 , or by enclosing the particularly in kinetically controlled systems. The influence of amorphous phase in an impermeable sheath of organic macromolecules on this process has not been generally macromolecules, such as polysaccharides[18] or mixtures of considered. polysaccharides and proteins rich in glutamic acid, threonine, We now discuss aggregation induced crystallization and and serine.[19,20] Thus a significant number of stabilized ACC extend this mechanism to inorganic organic hybrid building biominerals has now been documented in plant cystoliths,[21,22] blocks to highlight new insights into the design of synthesis snail shells,[23] ascidian spicules,[19,24] and crustacean exoskel routes to crystals with complex textures and morphologies, as etons.[25] In contrast, controlled phase transformation of ACC well as organized assemblies of organically interconnected results in the deposition of calcite spicules in sea urchin nanoparticles. larvae.[26,27] Interestingly, many biogenic calcites contain high levels (up to 30 mol%) of Mg2+ ions in the crystal lattice, and one possibility is that such high isomorphic substitution 3. Aggregation-Mediated Pathways of Crystal contents originate from associated Mg rich ACC precursors. Growth Although confirmation of these biogenic precursors has not yet been reported, laboratory experiments on calcite crystal The classical model of crystallization