Diastereoisomerism, Stability, and Morphology of Substituted meso-4-Sulfonatophenylporphyrin J-Aggregates,ACS Omega

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Diastereoisomerism, Stability, and Morphology of Substituted meso-4-Sulfonatophenylporphyrin J-Aggregates
ACS Omega ( IF 3.7 ) Pub Date : 2019-03-05 00:00:00 , DOI: 10.1021/acsomega.8b03176
Zoubir El-Hachemi _{1,

2} , Joaquim Crusats _{1,

2} , Carlos Troyano ₁ , Josep M. Ribó _{1,

2}

Affiliation

The comparison between nanoparticle morphologies of the J-aggregates of different meso-4-sulfonatophenylporphyrins showing non-sulfonato groups at some of the meso-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.

中文翻译：

取代的内消旋-4-磺基苯基卟啉J-聚集体的非对映异构性，稳定性和形态

不同内消旋-4-磺基苯基卟啉的J聚集体的纳米颗粒形态之间的比较，其中某些内消旋基团显示非磺基基团-位置构成了这个J族聚合体的基本自组装基序的2D晶体状特征的最终证明。源于J聚合二维片材的相对构型的战术性导致的非对映异构现象是决定溶液中显着的单分子层以及决定进一步生长时导致不同纳米粒子形态的分层途径的关键因素。由卟啉单元构成的这种大的单层片材的意想不到的稳定性可能是由在两个表面上由周围离子取代基的双层电势产生的载体引起的。这些双层电势在随后的单层3D生长中起着驱动作用，如本文中从立构规整性的决定性作用在J-聚集片材的稳定性及其向单层或双层纳米颗粒的演变中所推导的。当在聚集过程中剪切流体动力作用时，在颗粒的双电层上的力的稳定作用表明了这些力与先前报道的外消旋偏压的检测之间的关系。

更新日期：2019-03-05

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