Optical chemical sensors are widely applied in many fields of modern analytical practice, due to their simplicity in preparation and signal acquisition, low costs, and fast response time. Moreover, the construction of most modern optical sensors requires neither wire connections with the detector nor sophisticated and energy-consuming hardware, enabling wireless sensor development for a fast, in-field and online analysis. In this review, the last five years of progress (from 2017 to 2021) in the field of optical chemical sensors development for persistent organic pollutants (POPs) is provided. The operating mechanisms, the transduction principles and the types of sensing materials employed in single selective optical sensors and in multisensory systems are reviewed. The selected examples of optical sensors applications are reported to demonstrate the benefits and drawbacks of optical chemical sensor use for POPs assessment.

Reflectance anisotropy spectroscopy (RAS) has been largely used to investigate organic compounds: Langmuir–Blodgett and Langmuir–Schaeffer layers, the organic molecular beam epitaxy growth in situ and in real time, thin and ultrathin organic films exposed to volatiles, in ultra-high vacuum (UHV), in controlled atmosphere and even in liquid. In all these cases, porphyrins and porphyrin-related compounds have often been used, taking advantage of the peculiar characteristics of RAS with respect to other techniques. The technical modification of a RAS spectrometer (CD-RAS: circular dichroism RAS) allows us to investigate the circular dichroism of samples instead of the normally studied linear dichroism: CD-RAS measures (in transmission mode) the anisotropy of the optical properties of a sample under right and left circularly polarized light. Although commercial spectrometers exist to measure the circular dichroism of substances, the “open structure” of this new spectrometer and its higher flexibility in design makes it possible to couple it with UHV systems or other experimental configurations. The importance of chirality in the development of organic materials (from solutions to the solid state, as thin layers deposited—in liquid or in vacuum—on transparent substrates) could open interesting possibilities to a development in the investigation of the chirality of organic and biological layers. In this manuscript, after the detailed explanation of the CD-RAS technique, some calibration tests with chiral porphyrin assemblies in solution or deposited in solid film are reported to demonstrate the quality of the results, comparing curves obtained with CD-RAS and a commercial spectrometer.

The morphology of the film created by the aggregation of corrole molecules from ethanol solution onto the surface of gold substrate was studied by scanning tunneling microscopy both: (i) in situ, namely in quasi-equilibrium (wet sample), and (ii) ex situ, i.e., removing the substrate from the fluid cell and leaving the residual amount of solution on the substrate to desiccate (dry sample). Despite the different conditions, the morphology of the corrole overlayer formed on the film of molecules is reminiscent, in both cases, of the leopard skin; the "speckles" are actually areas where the molecular overlayer of flat molecules is not completed. We quantitatively compared these two similar morphologies by studying the power spectral density of the images, the fractal dimension D P of the hole perimeters, and the cumulative distribution function of the hole areas. We found that the last layer of both films, in spite of very different formation conditions, differed from each other only by a scale factor.