One-pot synthesis, crystallization and deracemization of isoindolinones from achiral reactants

The synthesis, crystallization, and complete solid-state deracemization of isoindolinones was realized in one pot simply by grinding achiral reaction components in a suitable solvent with an achiral catalyst. Previously, this concept was applied to a reversible reaction, but herein we showed that it could also be used in combination with reactions in which product formation is irreversible. A controlled final configuration of the product was obtained by using small amounts of chiral additives or seed crystals of the product

Twinning superlattices in indium phosphide nanowires

Here, we show that we control the crystal structure of indium phosphide (InP) nanowires by impurity dopants. We have found that zinc decreases the activation barrier for 2D nucleation growth of zinc-blende InP and therefore promotes the InP nanowires to crystallise in the zinc blende, instead of the commonly found wurtzite crystal structure. More importantly, we demonstrate that we can, by controlling the crystal structure, induce twinning superlattices with long-range order in InP nanowires. We can tune the spacing of the superlattices by the wire diameter and the zinc concentration and present a model based on the cross-sectional shape of the zinc-blende InP nanowires to quantitatively explain the formation of the periodic twinning.Comment: 18 pages, 4 figure

Epitaxial crystallization of insulin on an ordered 2D polymer template

Two-dimensional polymers (2DP) are a new class of materials that consist of a monolayer of ordered molecular building blocks, which have been covalently linked. One of these monomers was self-assembled on a flat muscovite mica scaffold and subsequently the organic layer was polymerized. The resulting flat and stable 2DP layer was used as a template for protein crystallization. Crystals of insulin were epitaxially grown on the template, whereas insulin crystals grown on clean muscovite mica had a random orientation. The template was selective, considering that no epitaxially ordered crystals formed of hen egg white lysozyme, bovine serum albumin, or talin

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/<i>kT</i>. At the lowest Δμ/<i>kT</i>, 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/<i>kT</i>, 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/<i>kT</i>. 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/<i>kT</i>, 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

Formation of a Salt Enables Complete Deracemization of a Racemic Compound through Viedma Ripening

Chiral purification is a very important step in the production of many products such as active pharmaceutical ingredients (API). These procedures are typically limited to a maximum yield of 50%. Methods that include a racemization method, such as Viedma ripening, offer a theoretical yield of 100%. Racemic conglomerate formation is a necessary condition for chiral purification processes that exploit crystallization, such as Viedma ripening. This condition forms a limiting factor because only 10% of the chiral organic molecules crystallize in this way; the other 90% form racemic compounds. For two compounds that crystallize as racemic compounds we demonstrate that salt formation can transform these into racemic conglomerates and show that these can subsequently be fully deracemized using Viedma ripening. Salt formation thus promises to be a crystal engineering tool to significantly extend the applicability of Viedma ripening

Noble metal surface degradation induced by organothiols

Copper, silver and gold layers evaporated on the muscovite mica (001) surface were exposed to a series of molecules containing an organothiol and/or a carboxylic acid chemical functional group to investigate the potential of these compounds to modify the surfaces. The surfaces were investigated using optical microscopy, atomic force microscopy, scanning electron microscopy, energy dispersive analysis of X-rays, and X-ray diffraction. Organothiols containing a carboxylic acid group were found to change the surface morphology drastically over a period of days, while molecules containing only one of these functional groups were usually not able to do so. The mechanism is most likely a reaction between the organothiol and the metal surface, forming a thermodynamically stable new compound. This finding could be of importance in the many applications where organothiols are used to functionalize noble metal surfaces