M. Mastroianni

Amination reaction on copper and germanium β-nitrocorrolates.

Copper and germanium complexes of β-substituted nitrocorroles were reacted with 4-amino-4H-1,2,4-triazole to give the corresponding β-amino-β-nitro derivatives, in moderate to good yields. This is the first successful example of a vicarious nucleophilic substitution performed on corrole derivatives, because the same reaction carried out on silver complexes afforded the corresponding 6-azahemiporphycenes by way of corrole ring expansion. The first step of this work is related to the modification of a synthetic protocol for preparation of the β-substituted nitro corroles. The nitration reaction was carried out on a copper corrole using NaNO(2) as the primary source of NO(2)(-) coupled with AgNO(2) used as oxidant. By variation of the molar ratio of the reagents it was possible to direct the product distribution toward mono- and dinitro derivatives. The reaction between mono- and dinitro derivatives of (TtBuCorrCu) with 4-amino-4H-1,2,4-triazole gave good results, leading to the isolation of 2-(NH(2))-3-(NO(2))-TtBuCorrCu and 2,18-(NH(2))(2)-3,17-(NO(2))(2)-TtBuCorrCu in moderate yields. To elucidate factors that influence the reaction, and to highlight the different behavior observed for different metal complex substrates, the electrochemistry of three copper complexes, TtBuPCorrCu, (NO(2))TtBuPCorrCu, and (NO(2))(2)TtBuPCorrCu, was studied by cyclic voltammetry and thin-layer UV-visible spectroelectrochemistry. The nitro groups on (NO(2))(x)TtBuPCorrCu are highly electron-withdrawing, which leads not only to a substantial positive shift of all redox potentials but also to a unique redox behavior and UV-vis spectrum of the singly reduced product as compared to the parent compound, TtBuPCorrCu. Finally, the amination reaction was carried out on a Ge(IV) nitrocorrolate, giving in good yield the 2-amino-3-nitroderivative, which was structurally characterized by single crystal X-ray crystallography.

Demetalation of Silver(III) Corrolates

Several procedures for the demetalation of silver(III) corrolates have been tested. Acidic conditions induce removal of the silver ion but they can also promote concomitant oxidation of the corrole nucleus to an isocorrole species, the degree of which will depend upon the specific acidic media. This oxidation cannot be completely avoided by addition of hydrazine, particularly in the case of 3-NO(2) substituted complexes which are quantitatively converted into the corresponding 3-NO(2), 5-hydroxy isocorroles upon silver ion removal. Several beta-nitro isocorrole products were isolated, and one was structurally characterized. Electrochemical and chemical reductive methods for silver(III) corrolates demetalation were then tested with the aim to avoid the formation of isocorroles. While reaction with sodium borohydride was shown to be quite effective to demetalate unsubstituted silver corrolates this was not the case for the beta-nitro derivatives where the peripheral nitro group is reduced by borohydride giving the corresponding 3-amino free base corrole species. For the beta-nitro corrole silver complexes, a successful approach was obtained using DBU/THF solutions which afforded the 3-NO(2) corrole free-base compound as a single reaction product in good yield. These conditions were also effective for unsubstituted corroles although longer reaction times were necessary in this case. To study in greater detail the corrole demetalation behavior, selected Ag(III) derivatives were characterized by cyclic voltammetry in pyridine, and the demetalation products spectrally characterized after controlled potential reduction in a thin-layer spectroelectrochemical cell.

EAT-by-LIGHT: Fiber-Optic and Micro-Optic Devices for Food Quality and Safety Assessment

A selection is presented of fiber-optic and micro-optic devices that have been designed and tested for guaranteeing the quality and safety of typical foods, such as extra virgin olive oil, beer, and milk. Scattered colorimetry is used to authenticate various types of extra virgin olive oil and beer, while a fiber-optic-based device for UV-VIS-NIR absorption spectroscopy is exploited in order to obtain the hyperspectral optical signature of olive oil. This is done not only for authentication purposes, but also so as to correlate the spectral data with the content of fatty acids, which are important nutritional factors. A micro-optic sensor for the detection of olive oil aroma that is capable of distinguishing different ageing levels of extra virgin olive oil is also presented. It shows effective potential for acting as a smart cap of bottled olive oil in order to achieve a nondestructive olfactory perception of oil ageing. Lastly, a compact portable fluorometer for the rapid monitoring of the carcinogenic M1 aflatoxin in milk, is experimented.

Beta-nitro derivatives of germanium(IV) corrolates.

The reaction between germanium(IV) meso-triphenylcorrolates and nitrate salts affords the corresponding beta-nitro substituted corroles in good yield. Chromatographic separation of the crude reaction mixtures enables isolation of a mu-oxo dimer along with the corresponding monomers bearing a hydroxy or methoxy group at an axial position of the germanium central metal ion. Depending on the reaction conditions, mono- or dinitro substituted complexes can be obtained. The substitution is highly regioselective in each case, giving only the 3-nitro or 3,17-dinitro derivative among the different possible isomers. Five of the synthesized complexes were examined by cyclic voltammetry and UV-visible spectroelectrochemistry in dichloromethane, and the dinitro mu-oxo dimer is structurally characterized.

6-Azahemiporphycene: a further example of corrole metamorphosis

The reaction of a corrole with 4-amino-4H-1,2,4-triazole affords an unprecedented 6-azahemiporphycene structure through macrocycle ring expansion; this is a further example of interconversion between different classes of tetrapyrroles.

Novel aspects of the chemistry of 1,19-diunsubstituted a,c- biladienes

Cyclization of a,c-biladienes in alcoholic solution gives corroles. When the same reaction is carried out in CHCl3 a completely different outcome is observed, and the product of the reaction is the corresponding open-chain biliverdin. The critical step for the cyclization to corrole is the formation of the fully conjugated 22,24-dihydro-a,b,c-bilatriene cation, which is allowed in methanol and appears to be prevented in CHCl3. The presence of substituents at the 10-position of the a,c-biladiene is also critical for the reaction; while a phenyl group strongly enhances the formation of corrole, in the case of alkyl groups the formation of both corrole and biliverdin is prevented. This result can reasonably be attributed to the failure to give a fully conjugated 22,24-dihydro-a,b,c-bilatriene structure for 10-alkyl substituted a,c-biladienes. Carrying out the a,c-biladiene cyclization in acidic methanol permits a new one-pot preparation of β-alkylcorroles.

EAT-by-LIGHT fiber-optic and micro-optic devices for food quality and safety assessment

A selection is presented of fiber-optic and micro-optic devices that have been designed and tested for guaranteeing the quality and safety of typical foods, such as extra virgin olive oil, beer, and milk. Scattered colorimetry is used to authenticate various types of extra virgin olive oil and beer, while a fiber-optic-based device for UV-VIS-NIR absorption spectroscopy is exploited in order to obtain the hyperspectral optical signature of olive oil. This is done not only for authentication purposes, but also so as to correlate the spectral data with the content of fatty acids, which are important nutritional factors. A micro-optic sensor for the detection of olive oil aroma that is capable of distinguishing different ageing levels of extra virgin olive oil is also presented. It shows effective potential for acting as a smart cap of bottled olive oil in order to achieve a non-destructive olfactory perception of oil ageing. Lastly, a compact portable fluorometer for the rapid monitoring of the carcinogenic M1 aflatoxin in milk, is experimented.

Non-destructive testing of olive oil off-flavors by means of a micro-optic smart cap

The design and experimental setup of a smart cap are presented. It is capable of sniffing the vapors of extra virgin olive oil, thus alerting the consumer or the retailer of any rancid flavor. The cap is made of an array of metalloporphyrin-based optochemical sensors, the colors of which are modulated by the concentration of aldehydes, the main responsible for rancid off-flavors. A micro-optic device, implemented to simulate a cap prototype, is presented. The spectral response of the chromophore-array is processed by means of multivariate data analysis so as to achieve an artificial olfactory perception of oil aroma and, consequently, an indication of oil ageing and rancidity. In practice, the cap prototype proved to be a device for non-destructive testing of bottled oil quality.

A smart cap for olive oil rancidity detection using optochemical sensors

The design and experimental setup of a smart cap are presented. It is capable of sniffing the vapors of extra virgin olive oil, thus alerting the consumer or the retailer of any rancid flavor. The cap is made of an array of metalloporphyrin-based optochemical sensors, the colors of which are modulated by the concentration of aldehydes, the main responsible for rancid off-flavors. A micro-optic device, implemented to simulate a cap prototype, is presented. The spectral response of the chromophore-array is processed by means of multivariate data analysis so as to achieve an artificial olfactory perception of oil aroma and, consequently, an indication of oil ageing and rancidity. In practice, the cap prototype proved to be a device for non-destructive testing of bottled oil quality.

Selectivity tailoring in molecular recognition based sensors: enhancement of metalloporphyrins sensitivity to hydrogen bond

Metalloporphyrins shown interesting properties as sensitive material for chemical sensors. In particular, they shown brilliant behaviours in electronic nose applications. From the point of view of this kind of applications it is necessary to differentiate sensor selectivity. In this paper, a method to enhance the selectivity of metalloporphyrins to hydrogen bond interacting compounds is illustrated. Furthermore, the structural modification of metalloporphyrin results in highly porous spatial arrangement of molecular films. This feature produces an improvement also at sensor sensitivity level. Modified metalloporphyrins were used to coat thickness shear mode resonators. The sensors were tested to different gases and results confirmed the enhanced responses to hydrogen bond interacting compounds such as alcohols