Total Alignment of Calcite at Acidic Polydiacetylene Films: Cooperativity at the Organic-Inorganic Interface

Abstract

Biological matrices can direct the absolute alignment of inorganic crystals such as calcite. Cooperative effects at an organic-inorganic interface resulted in similar co-alignment of calcite at polymeric Langmuir-Schaefer films of 10,12-pentacosadiynoic acid (p-PDA). The films nucleated calcite at the (012) face, and the crystals were co-aligned with respect to the polymer's conjugated backbone. At the same time, the p-PDA alkyl side chains reorganized to optimize the stereochemical fit to the calcite structure, as visualized by changes in the optical spectrum of the polymer. These results indicate the kinds of interactions that may occur in biological systems where large arrays of crystals are co-aligned.

Functional Self-Assembling Bolaamphiphilic Polydiacetylenes as Colorimetric Sensor Scaffolds

“…1 The intrinsic order and unique optical properties of self-assembling polydiacetylenes (PDAs), for instance, have attracted attention to these materials for direct sensing applications. 2,3 When properly aligned, diacetylene groups undergo UV-induced photopolymerization to form an ene-yne alternating polymer chain, resulting in organized structures (Fig. 1).…”

“…This unique chromatic property has also made polydiacetylenes promising candidates for colorimetric biosensors. 2,3,21 The architectures of amphiphilic PDA-based colorimetric biosensors reported to date were either vesicles in aqueous solutions 2,13 or thin films on solid supports generated using LangmuirBlodegtt or Langmuir-Schaefer methods, and incorporated ligands for detection of receptor binding (Fig. 1).…”

“…1). Amphiphilic diacetylene lipids have been polymerized to form single crystals, 4,5 Langmuir-Blodgett films, 3,[6][7][8] self-assembled monolayers, 9 and vesicles [10][11][12][13] and ribbons 14,15 in aqueous solution. Recently, immobilization of disulfide-modified PDA vesicles on gold surfaces 16 and amine-terminated vesicles on aldehyde-functionalized glass slides 17 were reported.…”

Long-lived photoexcited states in polydiacetylenes with different molecular and supramolecular organization

“…Among these polymers, the polydiacetylenes ͑PDA's͒ have enjoyed a period of renaissance [1][2][3][4][5][6][7][8][9][10][11][12][13][14] and the synthesis of novel PDA's has enlarged our knowledge on their properties, in particular, on the values of their nonlinear susceptibilities. 15,16 In the last five years we have been interested in the study of a class of attractive PDA's, the polycarbazolyldiacetylenes, 5,[17][18][19][20][21][22] in particular, of poly͓1,6-di ͑ N-carbazolyl͒-2,4-hexadiyne͔͑polyDCHD͒, 5,[19][20][21][22][23][24][25][26] which is, however, insoluble.…”

Crystallisation rates of calcite from an amorphous precursor in confinement

“…The results from this study offer a possible explanation for the dominance of (01.2)-oriented crystallisation on self-assembled monolayers and other organic substrates [30,31,32]. For instance, in the case of carboxylate terminated alkyl thiols, self-assembled on gold substrates, the headgroup spacing is almost perfectly commensurate with the (00.1) surface of calcite and yet the (01.2) face crystallises [9,30].…”