El-Hachemi Zoubir, Crusats Joaquim, Troyano Carlos, Ribó Josep M
Department of Inorganic and Organic Chemistry, Organic Chemistry Section, University of Barcelona, C. Martí i Franquès 1, E-08028 Barcelona, Catalonia, Spain.
Institute of Cosmos Science, Universitat de Barcelona (IEEC-ICC), C. Martí Franquès 1, E-08028 Barcelona, Catalonia, Spain.
ACS Omega. 2019 Mar 5;4(3):4804-4813. doi: 10.1021/acsomega.8b03176. eCollection 2019 Mar 31.
The comparison between nanoparticle morphologies of the J-aggregates of different -4-sulfonatophenylporphyrins showing non-sulfonato groups at some of the -positions constitutes an ultimate proof of the 2D crystal-like character of the basic self-assembly motif of this family of J-aggregates. Diastereoisomerism stemming from the tacticity of the relative configurations in relation to the J-aggregate bidimensional sheet is the key factor that determines both the striking monolayer in solution and also the hierarchical pathways leading to different nanoparticle morphologies upon further growth. The unexpected stability of such large monolayered sheets made up of porphyrin units is probably caused by the support originated at both surface faces by the double layer potentials of the peripheral ionic substituents. These double layer potentials play a driving role in the subsequent 3D growth of the monolayers, as deduced herein from the determining role of tacticity both in the stability of the J-aggregate sheet and in its evolution either to monolayered or to bilayered nanoparticles. The stabilizing role of the forces at the electrical double layer of the particle suggests a relationship between these forces and the previously reported detection of racemic biases when shear hydrodynamic forces are in action during the aggregation process.
不同的 -4-磺酰基苯基卟啉的 J-聚集体在某些 - 位置显示无磺酰基基团，其纳米颗粒形态之间的比较构成了这一家族 J-聚集体基本自组装基序二维晶体状特征的最终证据。源于相对于 J-聚集体二维片层相对构型的立构规整性的非对映异构现象是决定溶液中显著单层以及进一步生长时导致不同纳米颗粒形态的分级途径的关键因素。由卟啉单元构成的如此大的单层片层的意外稳定性可能是由外围离子取代基的双层电势在两个表面产生的支撑作用导致的。这些双层电势在单层随后的三维生长中起驱动作用，正如本文从立构规整性在 J-聚集体片层稳定性及其向单层或双层纳米颗粒演化中的决定性作用推断出来的那样。颗粒双电层处力的稳定作用表明这些力与先前报道的在聚集过程中剪切流体动力作用时外消旋偏差的检测之间存在关联。
