Complex ordered patterns in mechanical instability induced geometrically frustrated triangular cellular structures.

Geometrical frustration arises when a local order cannot propagate throughout the space because of geometrical constraints. This phenomenon plays a major role in many systems leading to disordered ground-state configurations. Here, we report a theoretical and experimental study on the behavior of buckling-induced geometrically frustrated triangular cellular structures. To our surprise, we find that buckling induces complex ordered patterns which can be tuned by controlling the porosity of the structures. Our analysis reveals that the connected geometry of the cellular structure plays a crucial role in the generation of ordered states in this frustrated system.

Formation of wurtzite InP nanowires explained by liquid-ordering.

We report an in situ surface X-ray diffraction study of liquid AuIn metal alloys in contact with zinc-blende InP (111)(B) substrates at elevated temperatures. We observe strong layering of the liquid metal alloy in the first three atomic layers in contact with the substrate. The first atomic layer of the alloy has a higher indium concentration than in bulk. In addition, in this first layer we find evidence for in-plane ordering at hollow sites, which could sterically hinder nucleation of zinc-blende InP. This can explain the typical formation of the wurtzite crystal structure in InP nanowires grown from AuIn metal particles.

From Ostwald ripening to single chirality.

A century ago Wilhelm Ostwald received the Nobel Prize for Chemistry. Although Ostwald was never significantly involved with the phenomenon of chirality, one of his discoveries, Ostwald ripening, is thought to be involved in a recently discovered method in which grinding-induced attrition is used to transform racemic conglomerates virtually quantitatively into a single enantiomer. In this Minireview the basic concepts developed by Ostwald will be introduced, followed by a summary of the current status of grinding-induced asymmetric transformations. We will see how close Ostwald himself came to discovering this technique.

Fast attrition-enhanced deracemization of naproxen by a gradual in situ feed.

Grind and cure: Using the nonsteroidal anti-inflammatory drug naproxen, a novel concept is demonstrated to dramatically enhance the rate of the recently discovered process of deracemization using abrasive grinding. The process relies on a gradual feed of the racemic target material by an in situ conversion.

Complete chiral resolution using additive-induced crystal size bifurcation during grinding.

Grinding them down: By using a tailor-made additive, even in the absence of racemization in solution, abrasive grinding can yield an enantiopure solid state. This novel chiral resolution technique is based on an asymmetric bifurcation in the crystal size distribution as a result of stereoselective hampered crystal growth. R = o-tolyl.

Epitaxy of Anthraquinone on (100) NaCl: A Quantitative Approach.

A growth cell suitable for microscopic in situ observation of well-controlled crystal growth from the vapor phase is used to study the heteroepitaxial growth of anthraquinone crystals on a (100) NaCl substrate. In this, the morphology, orientation, nucleation, and growth rate of the crystals is studied as a function of driving force, Δµ/kT. At the lowest Δµ/kT, the crystals are block-shaped and show no preferential orientation with respect to the substrate. Increasing the driving force leads to the growth of oriented block- and needle-shaped crystals, which nucleate from macrosteps on the substrate. At the highest Δµ/kT, crystals nucleate on the flat surface areas or at monatomic steps on the substrate, resulting in a dramatic increase in epitaxial needle density. Growth rate measurements show an exponential behavior as a function of Δµ/kT. In all cases, the supply of growth units proceeds via surface diffusion over the NaCl substrate surface toward the anthraquinone crystals. At the lowest Δµ/kT, growth is partly limited by integration of the growth units at the crystal surfaces. At intermediate driving force, kinetic roughening sets in, leading to rounded needle tips. At the highest supersaturation, growth is completely governed by the supply of growth units via surface diffusion, leading to tip splitting as a consequence of morphological instability.

Controlled growth and form of precipitating microsculptures.

Controlled self-assembly of three-dimensional shapes holds great potential for fabrication of functional materials. Their practical realization requires a theoretical framework to quantify and guide the dynamic sculpting of the curved structures that often arise in accretive mineralization. Motivated by a variety of bioinspired coprecipitation patterns of carbonate and silica, we develop a geometrical theory for the kinetics of the growth front that leaves behind thin-walled complex structures. Our theory explains the range of previously observed experimental patterns and, in addition, predicts unexplored assembly pathways. This allows us to design a number of functional base shapes of optical microstructures, which we synthesize to demonstrate their light-guiding capabilities. Overall, our framework provides a way to understand and control the growth and form of functional precipitating microsculptures.

Rationally designed complex, hierarchical microarchitectures.

The emergence of complex nano- and microstructures is of fundamental interest, and the ability to program their form has practical ramifications in fields such as optics, catalysis, and electronics. We developed carbonate-silica microstructures in a dynamic reaction-diffusion system that allow us to rationally devise schemes for precisely sculpting a great variety of elementary shapes by diffusion of carbon dioxide (CO2) in a solution of barium chloride and sodium metasilicate. We identify two distinct growth modes and show how continuous and discrete modulations in CO2 concentration, pH, and temperature can be used to deterministically switch between different regimes and create a bouquet of hierarchically assembled multiscale microstructures with unprecedented levels of complexity and precision. These results outline a nanotechnology strategy for "collaborating" with self-assembly processes in real time to build arbitrary tectonic architectures.

Buckling-induced reversible symmetry breaking and amplification of chirality using supported cellular structures.

Buckling-induced reversible symmetry breaking and amplification of chirality using macro- and microscale supported cellular structures is described. Guided by extensive theoretical analysis, cellular structures are rationally designed, in which buckling induces a reversible switching between achiral and chiral configurations. Additionally, it is demonstrated that the proposed mechanism can be generalized over a wide range of length scales, geometries, materials, and stimuli.

Asymmetric amplification in amino acid sublimation involving racemic compound to conglomerate conversion.

A straightforward unprecedented sublimation protocol that reveals both conversion of a racemic compound into a racemic conglomerate and subsequent enantioenrichment has been developed for the proteinogenic amino acid valine. The phenomenon has been observed in closed and open systems, providing insight into asymmetric amplification mechanisms under presumably prebiotic conditions.

Complete chiral symmetry breaking of an amino acid derivative directed by circularly polarized light.

Circularly polarized light (CPL) emitted from star-forming regions is an attractive candidate as a cause of single chirality in nature. It has remained difficult, however, to translate the relatively small chemical effects observed on irradiation of molecular systems with CPL into high enantiomeric excesses. Here we demonstrate that irradiation of a racemic amino acid derivative with CPL leads to a small amount of chiral induction that can be amplified readily to give an enantiopure solid phase. A racemate composed of equal amounts of left- and right-handed crystals in contact with the irradiated solution is converted completely into crystals of single-handedness through abrasive grinding when racemization is effected in the solution. The rotation sense of the CPL fully determines the handedness of the final solid state. These findings illustrate the potential effectiveness of CPL in the control of molecular asymmetry, which is relevant for the origin of the single chirality inherent to many biological molecules.

N,N-acetals as N-acyliminium ion precursors: synthesis and absolute stereochemistry of epiquinamide.

A stereoselective synthesis of (+)-epiquinamide is presented in combination with determination of the absolute configuration of the natural product. Key steps in the sequence involved chemoenzymatic formation of an enantiomerically pure cyanohydrin, reductive cyclization to the corresponding cyclic N,N-acetal, and subsequent conversion into a suitable N-acyliminium ion precursor to enable construction of the second ring.