Additive-controlled crystallization is wit-nessing a particularly rapid development and reveals a wealth of important infor-mation on crystallization mechanisms:
from the templating effect of insoluble additives to the selective adsorption effect of soluble additives, from homogeneous nucleation to heterogeneous nucleation, from nucleation promotion to inhibition, from prenucleation clusters to PILPs, from chiral resolution by chiral molecules to chiral nanosurface-based enantiose-lective crystallization, from Oswald ripening to oriented attachment or from single crystals to mesocrystals (see also the overview in Fig. 1). We expounded in this highlight on what is possible using various strategies and how to understand the mechanism of these strategies in order to launch a point of departure towards complicated control of crystallization using additives.
The possibilities in this field are tremendous and rapidly developing with increased understanding of the Fig. 41 (a) Schematic representation of the liquid diffusion experimental setup. SEM image and
TEM images of the two-dimensional superstructures obtained in the presence of [SDS]¼2 g L1, [Tween 20]¼2 g L1, and [Ca]¼10 mM, at 25C for 7 days: (b) SEM image of the fan-like units; (c) TEM image; (d) HRTEM image (right corner inset is the electron diffraction pattern).217Copyright 2009, American Chemical Society.
Fig. 42 SrCO3biomorphs prepared in a silica gel at pH 10.5 containing 0.01 M of carbonate ions in 6 h (a) and 9 h (b).219Copyright 2003, Elsevier. (c and d) CaCO3biomorphs prepared in a silica gel.220 Copyright 2008, American Chemical Society.
ª
underlying mechanisms. First and fore-most, the ongoing research on bio-minerals is providing more and more evidence for the synergy of different types of additves.71,185 Approaches to un-ravelling the mystery in nature must take that into account by a combination of additives222--224or additives with multiple functional blocks.225 Another significant challenge is how to obtain single crystal or mesocrystal based nanostructured composite materials with extraordinary properties.226,227Here again we can learn from nature. Studies of biominerals have produced a great deal of results to help us to interpret complex phenomena in bio-mineralization.19,228--233With nanocrystals as building blocks, oriented attachment and mesocrystal formation mechanisms show great promise at this end. In addi-tion, the production of synthetic organic single crystals with defined polymorph and morphology by additive controlled crystallization still remains difficult.
However, it is intriguing to note that the progress of basic research in the inorganic area also impacts the organic area.234,235 The distinctive properties of mesocrystals make them particularly appealing for the creation of advanced organic materials.
In summary, additives will be increas-ingly important for the control of crys-tallization reactions and the steadily increasing understanding of the under-lying mechanisms enables further prog-ress in this area. The field is moving forward from an empirical testing of the influence of various additives to an understanding of the role of additives in the crystallization process. In the fore-seeable future, it will likely even be possible to predict the outcome of an additive controlled crystallization reac-tion, which nowadays is still a major challenge for modeling approaches or even impossible. There is still much to be explored in this wide field in years to come.
Acknowledgements
R.Q.S. thanks the NIH (DE018335) for support of her current research.
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