Use of linear polymers to control the preparation of luminescent organic microcrystals

Langmuir. 2005 Jun 21;21(13):6030-7. doi: 10.1021/la046877j.

Abstract

Microcrystals of an organic fluorescent dye, 4-octylamino-7-nitrobenz-2-oxa-1,3-diazole, were generated using the reprecipitation method, which is a solvent exchange process. In the presence of polymers, namely, poly(acrylic acid), molecular weight 5100 g mol(-1) and 15 000 g mol(-1), and poly(acrylic acid-co-maleic acid), average molecular weight about 50 000 g mol(-1), used as their sodium salts, the reprecipitation process was strongly accelerated. The reprecipitation kinetics was monitored by UV/vis absorption spectroscopy and revealed a three-step mechanism, each step being influenced by the polymer. The size and shape of the microcrystals were analyzed by fluorescence microscopy. The microcrystals obtained in the presence of polymers were smaller and more regular than those prepared in water alone and were not agglomerated. When the polymer was placed in the reprecipitation medium before introducing the dye solution, the microcrystals displayed a rectangular shape. When the polymer was introduced 20 min after the beginning of the reprecipitation process, intricately structured flowerlike microcrystals were observed. Microanalysis revealed that the microcrystals contained noticeable amounts of polymer. The measurement of the surface electric zeta potential suggested that a proportion of the polymer was present at the microcrystal surface. This work gives a thorough insight into a field where trials have until now been performed in an empirical way. It opens new perspectives to produce low-cost organic microcrystals, potentially useful in optics or pharmaceutical sciences.