Changes in the proportions of an active pharmaceutical through cocrystals.

In this study, the modulation of amounts sulfathiazolium cations in different 2,6-pyridinedicarboxylates is demonstrated. An uncommon monoionic sulfathiazolium zinc 2,6-pyridinedicarboxylate (1:1 electrolyte) complex was characterized. Conventional sulfathiazolium zinc-bis-2,6-pyridinedicarboxylate dianionic complexes (2:1 electrolyte) were formed when hydroxyaromatic compounds such as 1,3-dihydroxybenzene or 3-nitrophenol were used as guest components. Thus, with the aid of the hydroxyaromatic molecules the zinc-bis-2,6-pyridinedicarboxylate complexes were stabilized with the relatively large sized sulfathiazolium cations. It was a consequence of domain expansion by the phenolic compounds. Sandwiched aromatic guests between the 2,6-pyridinedicarboxylates provided appropriate packing to accommodate the two large cations in the self-assemblies, which helped to modulate the amounts of sulfathiazole in different formulations. Antibacterial activities with E. coli DH5α have shown that the salt and the complexes have lower g/ml antibacterial activity than the parent drug.

Dual Modes and Dual Emissions of an Amino-Naphthoquinone Derivative.

3-(1,4-Dioxo-1,4-dihydronaphthalen-2-yl-amino)benzoic acid shows multiple tunable fluorescence emissions depending on solvent, pH and wavelength of excitation. Independent dual fluorescence emissions are observed while exciting compound 3-(1,4-dioxo-1,4-dihydronaphthalen-2-yl-amino)benzoic acid in UV-region or in visible region. In methanol at low concentration it shows both S1-S0 emission and ESIPT emission at 307 nm and 480 nm. Whereas in concentrated solution S1-S0 emission as well as dimer-like emission at 307 nm and 425 nm respectively are observed. Upon excitation in visible region, it shows two emission bands in visible region which are highly dependent on concentration and are attributed to charge transfer emission and emissions of anionic species. Modulations of these emissions by varying conditions are established.

Combinations of Tautomeric Forms and Neutral-Cationic Forms in the Cocrystals of Sulfamethazine with Carboxylic Acids.

The cocrystals of sulfamethazine with different acids, namely, 2-mercaptophenylcarboxylic acid, 2,6-pyridinedicarboxylic acid, 4-(4-hydroxyphenylazo)phenylcarboxylic acid, 3-(4-hydroxyphenyl)propanoic acid, and 4-(phenyl)phenylcarboxylic acid, are studied here. Each has distinct notable supramolecular features. The pyrimidin-2-amine unit of the sulfamethazine provided unique examples of cocrystals in which amidine and imidine forms or neutral and protonated forms of sulfamethazine are observed in 2:2 ratios. Hence, this study provides avenues to explore cocrystals with tautomeric forms together in a cocrystal and also neutral and protonated cocrystal partners as apparent multicomponents in cocrystals. Among the cocrystals, three of them have the amidine form of the sulfamethazine in respective self-assembly. The cocrystal of 2-mercapto-phenylcarboxylic acid with sulfamethazine has the amidine form and it has the distinction of having S-H···π interactions. The cocrystal of sulfamethazine with 2,6-pyridinecarboxylic acid is a rare example of a 1:1 cocrystal of sulfmethazine with dicarboxylic acid. It has methanol molecules as a solvent of crystallization. Sulfamethazine forms a hydrated cocrystal with 4-(4-hydroxyphenylazo)-phenylcarboxylic acid that has conventional R 2 2(8) synthons of amidine hydrogen-bonding with carboxylic acid. The phenolic part of the acid component is anchored to the water molecule and provides a robust self-assembly. The hydrated cocrystal of sulfamethazine with 3-(4-hydroxyphenyl)propanoic acid (2:2 cocrystal) has two independent molecules of sulfamethazine, one in amidine form and the other in imidine form. It has two neutral carboxylic acids anchored through complementary hydrogen bonds and also has two water molecules of crystallization. The cocrystal of sulfamethazine with 4-(phenyl)phenylcarboxylic acid is also a 2:2 cocrystal. It is a di-hydrate, which has a neutral and protonated form of sulfamethazine. The neutral form is hydrogen-bonded to a neutral carboxylic acid, whereas the protonated form is charge-assisted hydrogen-bonded to the corresponding carboxylate anion.

Stacking among the clips of the poly-aromatic rings of phenazine with hydroxy-aromatics and photophysical properties.

Clip-like arrangements of molecules in the cocrystals of phenazine with hydroxy-aromatics in their respective self-assemblies and photophysical properties were presented. Phenazine cocrystals with 1,2-dihydroxybenzene provided assembly with butterfly-like arrangements. In these cocrystals, the phenazine molecules occurred in parallel pairs having extensive π-stacking. The clip-like cocrystals with 1,3-dihydroxybenzene also exhibited parallel pairs of phenazine molecules that were parallel cofacial π-stacked. The hydrated cocrystals of phenazine with 1,2,3-trihydroxybenzene had chains of parallel cofacial phenazine rings having three distinguishable π-separation distances among the centroids of the phenazine rings. Also, 2,7-dihydroxynaphthalene formed a clip-like cocrystal with phenazine, which encapsulated an additional molecule of phenazine. This cocrystal also provided chain-like parallel arrangements of the phenazine molecules. The emission and quantum yields of the cocrystals were determined by the integrating sphere method, which indicated that only the cocrystal of phenazine with 2,7-dihydroxynaphthalene showed monomer-like emission of phenazine and the rest of the cocrystals were in a quenched state. In the solution phase, quenching of the emission of hydroxynaphthalene was observed when phenazine was added to an independent solution of 2,7-dihydroxynaphthalene or another hydroxynaphthalene. However, when hydroxybenzenes were added to a solution of phenazine, fluorescence enhancements of phenazine occurred due to photo-electron transfer.