Snapshot circular dichroism measurements

Two coherent waves carrying orthogonal polarizations do not interfere when they superpose, but an interference pattern is generated when the two waves share a common polarization. This well-known principle of coherence and polarization is exploited for the experimental demonstration of a novel method for performing circular dichroism measurements whereby the visibility of the interference fringes is proportional to the circular dichroism of the sample. Our proof-of-concept experiment is based upon an analog of Young's double-slit experiment that continuously modulates the polarization of the probing beam in space, unlike the time modulation used in common circular dichroism measurement techniques. The method demonstrates an accurate and sensitive circular dichroism measurement from a single camera snapshot, making it compatible with real-time spectroscopy

Role of the hydrophobic effect in the transfer of chirality from molecules to complex systems. From chiral surfactants to porphyrin/surfactant aggregates

The interaction between the achiral sulfonated porphyrin 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin, H2TPPS4, and two chiral cationic surfactants has been studied by optical absorption, fluorescence, and circular dichroism (CD) spectroscopies. At surfactant concentrations above the critical micellar concentration (cmc) the porphyrin is included in the micellar aggregates, but it is CD silent. Below the cmc at a definite porphyrin/surfactant stoichiometry the formation of heteroaggregates with transfer of chirality to the porphyrin chromophore occurs. The preferred surfactant/porphyrin stoichiometry is 3:1, which suggests a structure driven by electrostatic and hydrophobic interactions between porphyrin and surfactant and dipolar and ionic interactions with the water solution. At surfactant concentrations above the cmc, depending on the protocol of preparation of the samples, the formation of the two kinds of aggregates can be observed, reversible for the simple surfactant micelles incorporating the porphyrin, but irreversible for the heteroaggregates

Case history of porphyrin J-aggregates: a personal point of view

The formation and structure of the title aggregates are paradigms of the self-assembly of amphiphilic molecular building blocks in supramolecular chemistry. This review summarizes the research in the University of Barcelona on the homoassociation of the water soluble meso 4-sulfonatophenyl-and phenyl substituted porphyrins

5-Phenyl-10,15,20-tris(4-sulfonatophenyl)porphyrin: Synthesis, catalysis and structural studies

A convenient protocol for the preparation of 5-phenyl-10,15,20-tris(4-sulfonatophenyl) porphyrin, a water-soluble porphyrin with unique aggregation properties, is described. The procedure relies on the one-pot reductive deamination of 5-(4-aminophenyl)-10,15,20-tris(4-sulfonatophenyl)porphyrin, that can be in turn easily obtained from 5,10,15,20-tetraphenylporphyrin by a known three-step sequence involving mononitration, nitro to amine reduction and sulfonation of the phenyl groups. This method provides the title porphyrin in gram scale, and compares very favorably with the up to now only described procedure based on the partial sulfonation of TPP, that involves a long and tedious chromatographic enrichment of the final compound. This has allowed us to study for the first time both the use of its zwitterionic aggregate as a supramolecular catalyst of the aqueous Diels-Alder reaction, and the morphology of the aggregates obtained under optimized experimental conditions by atomic force microscopy and also by transmission electron cryomicroscopy

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

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

Formation of an epitaxial monolayer on graphite upon short-time surface contact with highly diluted aqueous solutions of 1-monostearoylglycerol

Short-time surface contact of highly diluted 1-monostearoylglycerol (1-MSG) aqueous solutions with highly oriented pyrolitic graphite results in the deposition of an epitaxial monolayer that can be detected by atomic force microscopy operating in tapping mode at the graphite-air interface. The monolayer obtained with the racemic mixture is then compared to that obtained with one of the pure enantiomers. The analogous behavior found for aqueous solutions of rac-1-MSG and 3-sn-MSG implies a two-dimensional self-assembly process with chiral discrimination. The results suggest that the monolayer originates from species located at the surface of the deposition drop. They also indicate that the simple experimental procedure reported, or more elaborate Langmuir-Schaefer methods, could be the method of choice to prepare other monolayers of similar surfactants

Metastability in supersaturated solution and transition towards chirality in the crystallization of NaClO3

Analysis of the chiral composition of the crystal mixture obtained from samples of boiling solutions of NaClO3 (see picture) indicates that symmetry breaking towards homochiral compositions may begin in the metastable stage preceding crystallization, that is, at the level of subcritical clusters

Mirror symmetry breaking with limited enantioselective autocatalysis and temperature gradients: a stability survey

We analyze limited enantioselective (LES) autocatalysis in a temperature gradient and with internal flow/recycling of hot and cold material. Microreversibility forbids broken mirror symmetry for LES in the presence of a temperature gradient alone. This symmetry can be broken however when the auto-catalysis and limited enantioselective catalysis are each localized within the regions of low and high temperature, respectively. This scheme has been recently proposed as a plausible model for spontaneous emergence of chirality in abyssal hydrothermal vents. Regions in chemical parameter space are mapped out in which the racemic state is unstable and bifurcates to chiral solutions

Structure vs. excitonic transitions in self-assembled porphyrin nanotubes and their effect on light absorption and scattering

The optical properties of diprotonated meso-tetrakis(4-sulphonatophenyl)porphyrin (TPPS4) J-aggregates of elongated thin particles (nanotubes in solution and ribbons when deposited on solid interfaces) are studied by different polarimetric techniques. The selective light extinction in these structures, which depends on the alignment of the nanoparticle with respect to the polarization of light, is contributed by excitonic absorption bands and by resonance light scattering. The optical response as a function of the polarization of light is complex because, although the quasi-one-dimensional structure confines the local fields along the nanotube axis, there are two orthogonal excitonic bands, of H- and J-character, that can work in favor of or against the field confinement. Results suggest that resonance light scattering is the dominant effect in solid state preparations, i.e. in collective groups (bundles) of ribbons but in diluted solutions, i.e. with isolated nanotubes, the absorption at the excitonic transitions remains dominant and linear dichroism spectra can be a direct probe of the exciton orientations. Therefore, by analyzing scattering and absorption data we can determine the alignment of the excitonic bands within the nanoparticle, i.e. of the orientation of the basic 2D porphyrin architecture in the nanoparticle. This is a necessary first step for understanding the directions of energy transport, charge polarization and non-linear optical properties in these materials