M. Amparo F. Faustino

Corroles as anion chemosensors: exploiting their fluorescence behaviour from solution to solid-supported devices

The reactivity of the new gallium(III) complex of 3-vinyl-5,10,15-tris(pentafluorophenyl)corrole 4, as a diene in Diels–Alder reactions was studied using 1,4-benzoquinone and 1,4-naphthoquinone as dienophiles. In these reactions only the dehydrogenated adducts 5 and 6 were isolated. All the new corrole derivatives 4–6 were fully characterized by elemental analysis, 1H-NMR, 13C-NMR, 19F-NMR, MALDI-TOF-MS, UV-Vis absorption and emission spectroscopy. The sensing ability of compounds 4–6 and of their precursors 1–3 was studied in solution towards the spherical halide ions F−, Cl−, Br−, I−, the linear anion CN− and the bulky anions CH3COO− and H2PO4−. This study was also realized in gas-phase with the anions F− and CN−. A red-shift in the absorption spectra and an enhancement in the emission intensity were observed, with compounds 1, 3 and 5 being strongly sensitive to fluoride. The highest association constant was obtained for 1 with F−, being able to quantify 0.69 ppm of this anion. On the other hand, compounds 1 and 2 present a high sensitivity towards cyanide anions, producing a red-shift in the absorption and emission spectra and an increase in the emission intensity, being able to quantify a minimal amount of 1.43 ppm. Moreover, compounds 1 and 5 were used to prepare two low-cost solid polymers, based on polymethylmethacrylate (PMMA) and polyacrylamide, the last one being very promising since it is able to detect ca. 70.0 ppb of CN− in water. Compounds 2a and 5 were also tested in the presence of 4,4′-bipyridine, caffeine and nicotine and compound 2a proved to be very sensitive to 4,4′-bipyridine, while compound 5 was really effective for detecting caffeine and nicotine.

Strategies for Corrole Functionalization

This review covers the functionalization reactions of meso-arylcorroles, both at the inner core, as well as the peripheral positions of the macrocycle. Experimental details for the synthesis of all known metallocorrole types and for the N-alkylation reactions are presented. Key peripheral functionalization reactions such as halogenation, formylation, carboxylation, nitration, sulfonation, and others are discussed in detail, particularly the nucleophilic aromatic substitution and the participation of corroles in cycloaddition reactions as 2π or 4π components (covering Diels-Alder and 1,3-dipolar cycloadditions). Other functionalizations of corroles include a large diversity of reactions, namely Wittig reactions, reactions with methylene active compounds, formation of amines, amides, and imines, and metal catalyzed reactions. At the final section, the reactions involving oxidation and ring expansion of the corrole macrocycle are described comprehensively.

Corrole and corrole functionalized silica nanoparticles as new metal ion chemosensors: a case of silver satellite nanoparticles formation.

Corrole macrocycles are very appealing dyes for incorporation into light harvesting devices. This work shows the sensorial ability of 5,10,15-tris(pentafluorophenyl)corrole 1 and its monoanionic species toward Na(+), Ca(2+), Cu(2+), Cd(2+), Pb(2+), Hg(2+), Ag(+), and Al(3+) metal ions in toluene and acetonitrile. The photophysical studies toward metal ions were carried out by absorption and emission spectroscopy. From all metal ions studied, corrole 1 shows to be colorimetric for Hg(2+) allowing a naked-eye detection of Hg(2+) through a change of color from purple to blue in acetonitrile and from green to yellow in toluene. In addition a new β-imine corrole 4 was successful synthesized and further functionalized with 3-isocyanatopropyl-trimethoxysilane resulting in an alkoxysilane derivative 5. The grafting of alkoxysilane derivative 5 with optically transparent silica nanoparticles (SiNPs) was achieved succesfully. The new-coated silica nanoparticles with corrole 5 were studied in the presence of Cu(2+), Hg(2+), and Ag(+) as metal ion probes. Interestingly, upon addition of Ag(+), groups of satellite AgNPs were formed around the SiNPs and were checked by transmission electron microscopy (TEM). At same time, a change of color from green to yellow was observed.

Synthesis, Spectroscopy Studies, and Theoretical Calculations of New Fluorescent Probes Based on Pyrazole Containing Porphyrins for Zn(II), Cd(II), and Hg(II) Optical Detection

New pyrazole-porphyrin conjugates were successfully prepared from a reaction of β-porphyrin-chalcone derivatives with phenylhydrazine in acetic acid followed by an oxidative step. This fast and efficient synthetic approach provided the expected compounds in yields up to 82%. The sensing ability of the new porphyrin-pyrazole derivatives to detect the metal ions Ag(+), Na(+), K(+), Mg(2+), Ca(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Cr(3+) was studied by spectrophotometric and spectrofluorimetric titrations. In the presence of Zn(2+), the conjugates exhibit changes in the emission spectra that are desired for a ratiometric-type fluoroionophoric detection probe. The studies were extended to gas phase, where the pyrazole-porphyrin conjugates show ability to sense metal ions with high selectivity toward Cu(2+) and Ag(+), and in poly(methyl methacrylate) doped films with promising results for Zn(2+) detection.

Photodynamic inactivation of bioluminescent Escherichia coli by neutral and cationic pyrrolidine-fused chlorins and isobacteriochlorins

Photodynamic inactivation of bioluminescent Escherichia coli in the presence of cationic chlorin and isobacteriochlorin photosensitizers (PSs) obtained from 5,10,15,20-tetrakis(pentafluorophenyl)-porphyrin is described. The spectroscopic data for the neutral and cationic derivatives and their photophysical characterizations, especially fluorescence and singlet oxygen generation capacity are also reported. The results show that there is a direct relation between the inactivation efficiency and the increasing number of charges on the molecules. The combined effect of higher wavelength absorption and number of positive charges on the PS shows a 6.1 log reduction during the inactivation process. Overall this study shows that the cationic isobacteriochlorin has high potential to be used as PS for the inactivation of Gram (-) bacteria.

A New 3,5-Bisporphyrinylpyridine Derivative as a Fluorescent Ratiometric Probe for Zinc Ions

A new 3,5-disubstituted pyridine with two porphyrin moieties was prepared through an efficient synthetic approach involving 2-formyl-5,10,15,20-tetraphenylporphyrin (1), piperidine, and catalytic amounts of [La(OTf)3]. 3,5-Bis(5,10,15,20-tetraphenylporphyrin-2-ylmethyl)pyridine (2) was fully characterized and its sensing ability towards Zn(2+), Cu(2+), Hg(2+), Cd(2+), and Ag(+) was evaluated in solution by absorption and fluorescence spectroscopy and in gas phase by using matrix-assisted laser desorption/ionization (MALDI)-TOF mass spectrometry. Strong changes in the ground and excited state were detected in the case of the soft metal ions Zn(2+), Cd(2+), Hg(2+), and Cu(2+). A three-metal-per-ligand molar ratio was obtained in all cases and a significant ratiometric behavior was observed in the presence of Zn(2+) with the appearance of a new band at 608 nm, which can be assigned to a metal-to-ligand charge transfer. The system was able to quantify 79 ppb of Zn(2+) and the theoretical calculations are in accordance with the stoichiometry observed in solution. The gas-phase sensorial ability of compound 2 towards all metal ions was confirmed by using MALDI-TOF MS and in solid state by using polymeric films of polymethylmethacrylate (PMMA) doped with ligand 2. The results showed that compound 2 can be analytically used to develop new colorimetric molecular devices that are able to discriminate between Hg(2+) and Zn(2+) in solid phase. The crystal structure of Zn(II) complex of 3,5-bisporphyrinylpyridine was unequivocally elucidated by using single-crystal X-ray diffraction studies.

Preparation and ion recognition features of porphyrin–chalcone type compounds as efficient red-fluorescent materials

A series of porphyrins containing an α,β-unsaturated ketone unit in a β-pyrrolic position (4a–e) were synthesized and characterized. Their sensing ability towards Ag+, Cu2+, Zn2+, Cd2+, and Hg2+ was evaluated in solution by absorption and fluorescence spectroscopy and in the gas phase using MALDI-TOF-MS spectrometry. The versatility of these types of compounds towards other metals was also analysed by studying the behaviour of compound 4d in the presence of Na+, K+, Tl+, Ca2+, Mg2+, Mn2+, Co2+, Ni2+, Pb2+, Fe2+, Fe3+, Cr3+ and Al3+. Polymeric films of polymethylmethacrylate (PMMA) doped with ligand 4d were prepared and their ability to be used as metal ion-probes in the solid state was studied. Compounds of type 4 showed the best performance to be analytically used in developing new Zn2+ ratiometric molecular devices.

Synthesis of new chlorin e6 trimethyl and protoporphyrin IX dimethyl ester derivatives and their photophysical and electrochemical characterizations.

In view of increasing demands for efficient photosensitizers for photodynamic therapy (PDT), we herein report the synthesis and photophysical characterizations of new chlorin e6 trimethyl ester and protoporphyrin IX dimethyl ester dyads as free bases and Zn(II) complexes. The synthesis of these molecules linked at the β-pyrrolic positions to pyrano[3,2-c]coumarin, pyrano[3,2-c]quinolinone, and pyrano[3,2-c]naphthoquinone moieties was performed by using the domino Knoevenagel hetero Diels-Alder reaction. The α-methylenechromanes, α-methylenequinoline, and ortho-quinone methides were generated in situ from a Knoevenagel reaction of 4-hydroxycoumarin, 4-hydroxy-6-methylcoumarin, 4-hydroxy-N-methylquinolinone, and 2-hydroxy-1,4-naphthoquinone, respectively, with paraformaldehyde in dioxane. All the dyads as free bases and as Zn(II) complexes were obtained in high yields. All new compounds were fully characterized by 1D and 2D NMR techniques, UV/Vis spectroscopy, and HRMS. Their photophysical properties were evaluated by measuring the fluorescence quantum yield, the singlet oxygen quantum yield by luminescence detection, and also the triplet lifetimes were correlated by flash photolysis and intersystem crossing (ISC) rates. The fluorescence lifetimes were measured by a time-correlated single photon count (TCSPC) method, fluorescence decay associated spectra (FDAS), and anisotropy measurements. Magnetic circular dichroism (MCD) and circular dichroism (CD) spectra were recorded for one Zn(II) complex in order to obtain information, respectively, on the electronic and conformational states, and interpretation of these spectra was enhanced by molecular orbital (MO) calculations. Electrochemical studies of the Zn(II) complexes were also carried out to gain insights into their behavior for such applications.

Revisiting Heck–Mizoroki reactions in ionic liquids

The use of ionic liquids as an alternative to conventional organic solvents has been an important research topic in order to answer economic and environmental challenges. This critical review revisits the different approaches and achievements on the use of ionic liquids as solvents in Heck–Mizoroki coupling reactions; a brief reference to supported ionic liquids will be also highlighted.

Electrospray Tandem Mass Spectrometry of β-Nitroalkenyl Meso-Tetraphenylporphyrins

β-Nitroalkenyl meso-tetraphenylporphyrins [β-TPPCHC(NO2)R)], as free-bases and Zn(II) complexes, were studied by electrospray mass spectrometry (ESI-MS). Under this ionisation condition the [M + H]+ ions are formed. The fragmentation pattern of the resulting [M + H]+ ions were studied by electrospray tandem mass spectrometry (ESI-MS/MS). The ESI-MS/MS of β-nitroalkenylporphyrins, either as free-bases or as Zn(II) complexes, show several interesting features, distinct from the typical behaviour of nitro compounds. For the studied compounds, common main fragmentation patterns are observed, namely characteristic losses of NO2•, HNO2, 2OH•, RNO2, RCNO, RCNO2, RCH2NO2, C6H5• plus NO2• and the formation of the protonated macrocycle, [TPP + H]+ or [ZnTPP + H]+. However, depending on the presence or absence of the metal and the nature of the R substituent, important differences are observed on the relative abundances of the ions formed by the same fragmentation pathway. The presence of bromine in the alkenyl group leads to a peculiar behaviour, since the main fragmentation pattern corresponds to the combined elimination of the bromine atom with the typical nitro group fragments. When R = Br, the loss of the nitro group occurs in low relative abundance (11-16%). However, when R = CH3, the relative abundance of the ion due to the loss of HNO2 changes drastically from 100%, observed for the free-base porphyrin, to 29% in the case of the Zn(II) complex. These variations of the relative abundance of the fragment corresponding to the loss of the nitro moiety (typically considered as a diagnostic fragment) can induce to an erroneous interpretation of their MS/MS spectra. Some fragmentations are observed only for the free-base porphyrins, namely the loss of •CH(NO2)R and HNO2 plus C2H2, while the loss of OH•, H2O, OH• plus H2O and RCCH plus H2O is observed only for the complexes. Unusual and unexpected fragmentations are also observed, namely the losses of RCNO, RCNO2 and HNO2 plus C2H2. This work demonstrates that valuable structural information about the β-nitroalkenyl substituents linked to meso-tetraarylporphyrins can be achieved using MS/MS. These results can also be useful for the interpretation of the mass spectra of other nitroalkenyl substituted compounds.