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The reaction of Zn ions with β-octaalkylcorroles leads to the air oxidation of the macrocycle, with the formation of a mixture of 5- and 10-oxocorroles. Spectroscopic characterization confirms the antiaromatic character of these macrocycles. A simple synthetic protocol opens the way for more detailed studies of oxocorrole chemistry.

The versatility of metal complexes of corroles has raised interest in the use of these molecules as elements of chemical sensors. The tuning of the macrocycle properties via synthetic modification of the different components of the corrole ring, such as functional groups, the molecular skeleton, and coordinated metal, allows for the creation of a vast library of corrole-based sensors. However, the scarce conductivity of most of the aggregates of corroles limits the development of simple conductometric sensors and requires the use of optical or mass transducers that are rather more cumbersome and less prone to be integrated into microelectronics systems. To compensate for the scarce conductivity, corroles are often used to functionalize the surface of conductive materials such as graphene oxide, carbon nanotubes, or conductive polymers. Alternatively, they can be incorporated into heterojunction devices where they are interfaced with a conductive material such as a phthalocyanine. Herewith, we introduce two heterostructure sensors combining lutetium bisphthalocyanine (LuPc 2 ) with either 5,10,15-tris(pentafluorophenyl) corrolato Cu ( 1 ) or 5,10,15-tris(4-methoxyphenyl)corrolato Cu ( 2 ). The optical spectra show that after deposition, corroles maintain their original structure. The conductivity of the devices reveals an energy barrier for interfacial charge transport for 1 /LuPc 2 , which is a heterojunction device. On the contrary, only ohmic contacts are observed in the 2 /LuPc 2 device. These different electrical properties, which result from the different electron-withdrawing or -donating substituents on corrole rings, are also manifested by the opposite response with respect to ammonia (NH 3 ), with 1 /LuPc 2 behaving as an n-type conductor and 2 /LuP C2 behaving as a p-type conductor. Both devices are capable of detecting NH 3 down to 10 ppm at room temperature. Furthermore, the sensors show high sensitivity with respect to relative humidity (RH) but with a reversible and fast response in the range of 30-60% RH.

The coordination chemistry of corrole has witnessed a great improvement in the past few years and its Periodic Table has been widened to be so large that it is compared with that of porphyrins. However, Ni and Zn ions, commonly used with porphyrins for both synthetic and theoretical purposes, are sparsely reported in the case of corroles. Here, we report synthetic protocols for preparing Ni and Zn triarylcorrole complexes. In the case of Zn, the preliminary oxidation of the free base corrole in DMSO to the neutral corrole radical is a necessary step to obtain the coordination of the metal ion, because the direct reaction led to the formation of an open-chain tetrapyrrole. The Ni complex could be directly obtained by heating the free base corrole and Ni(II) salt to 100 °C in a DMSO solution containing FeCl 3 . The non-innocent nature of the corrole ligand for both complexes has been elucidated by EPR, and in the case of the Zn derivative the first spectroelectrochemical characterization is presented.

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.

Volatolomics is gaining consideration as a viable approach to diagnose several diseases, and it also shows promising results to discriminate COVID-19 patients via breath analysis. This paper extends the study of the relationship between volatile compounds (VOCs) and COVID-19 to blood serum. Blood samples were collected from subjects recruited at the emergency department of a large public hospital. The VOCs were analyzed with a gas chromatography mass spectrometer (GC/MS). GC/MS data show that in more than 100 different VOCs, the pattern of abundances of 17 compounds identifies COVID-19 from non-COVID with an accuracy of 89% (sensitivity 94% and specificity 83%). GC/MS analysis was complemented by an array of gas sensors whose data achieved an accuracy of 89% (sensitivity 94% and specificity 80%)., Competing Interests: The authors declare no competing interests., (© 2021 The Authors.)

The reaction of 5,10,15-tritolylcorrole with 3-dimethylaminoacrolein (3-DMA) and POCl 3 gives a further example of the rebel reactivity of this contracted macrocycle. While no evidence was obtained for the formation of the expected β-acrolein corrole, the inner core substituted N21,N22-3-formylpropylcorrole and the 10-acrolein isocorrole were the reaction products. By increasing the temperature or the amount of the Vilsmeier reagent, the 10-isocorrole became the unique reaction product. The formation of the isocorrole by electrophilic attack of the Vilsmeier reagent to the 10-position of the corrole is unprecedented in the porphyrinoids field and it could pave the way for a novel route to the preparation of stable isocorroles.