Surface transport mechanisms in molecular glasses probed by the exposure of nano-particles.

For a glass-forming liquid, the mechanism by which its surface contour evolves can change from bulk viscous flow at high temperatures to surface diffusion at low temperatures. We show that this mechanistic change can be conveniently detected by the exposure of nano-particles native in the material. Despite its high chemical purity, the often-studied molecular glass indomethacin contains low-concentration particles approximately 100 nm in size and 0.

Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.

Despite an absence of conventional porosity, the 1D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 ] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 (ROH)2 ] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.

Fast surface crystallization of molecular glasses: creation of depletion zones by surface diffusion and crystallization flux.

Molecular glasses can grow crystals much faster at the free surface than in the interior. A property of this process is the creation of depressed grooves or depletion zones around the crystals on the initially flat amorphous surface. With scanning electron microscopy and atomic force microscopy, we studied this phenomenon in indomethacin, which crystallizes in two polymorphs (α and γ) of different morphologies.

Fast Surface Crystal Growth on Molecular Glasses and Its Termination by the Onset of Fluidity.

Organic glasses can grow crystals much faster on the free surface than in the interior, a phenomenon important for fabricating stable amorphous materials. This surface process differs from and is faster than the glass-to-crystal (GC) growth mode existing in the bulk of molecular glasses. We report that similar to GC growth, surface crystal growth terminates if glasses are heated to gain fluidity.

Termination of Solid-State Crystal Growth in Molecular Glasses by Fluidity.

Fast crystal growth can abruptly emerge as molecular liquids are cooled to become glasses, a phenomenon presently unknown for other materials. This glass-to-crystal (GC) mode can cause crystallization rates orders of magnitude faster than those predicted by standard models. While GC growth is known for 12 systems, its features vary greatly with growth rates spanning a factor of 10(4).

Anticounterfeit protection of pharmaceutical products with spatial mapping of X-ray-detectable barcodes and logos.

Counterfeit pharmaceutical products are a global threat to public health, and they undermine the credibility and the financial success of the producers of genuine products. The escalating circulation of counterfeit drugs demands new anticounterfeit measures that permit rapid screening, are nondestructive, and cannot be circumvented easily. Herein we describe a micro-X-ray diffraction (μ-XRD) protocol for this purpose capable of reading barcodes and logos fabricated on various substrates using soft-lithography stamping of compounds that can be read by X-ray diffraction but are invisible to the naked eye or optical microscopy.

Chemical double mutant cycles for the quantification of cooperativity in H-bonded complexes.

Chemical double mutant cycles have been used in conjunction with new H-bonding motifs for the quantification of chelate cooperativity in multiply H-bonded complexes. The double mutant cycle approach specifically deals with the effects of substituents, secondary interactions, and allosteric cooperativity on the free energy contributions from individual H-bond sites and allows dissection of the free energy contribution due to chelate cooperativity associated with the formation of intramolecular noncovalent interactions. Two different doubly H-bonded motifs were investigated in carbon tetrachloride, chloroform, 1,1,2,2-tetrachloroethane, and cyclohexane, and the results were similar in all cases, with effective molarities of 3-33 M for formation of intramolecular H-bonds.