Hybrid Zn-ß-Aminoporphyrin-Carbon Nanotubes: Pyrrolidine and Direct Covalent Linkage Recognition, and Multiple-Photo Response.

To unveil and shape the molecular connectivity in (metallo)porphyrin-carbon nanotube hybrids are of main relevance for the multiple medicinal, photoelectronic, catalytic, and photocatalytic applications of these materials. Multi-walled carbon nanotubes (MWCNTs) were modified through 1,3-dipolar cycloaddition reactions with azomethine ylides generated in situ and carrying pentafluorophenyl groups, followed by immobilization of the ß-amino-tetraphenylporphyrinate Zn(II). The functionalities were confirmed via XPS and FTIR, whereas Raman spectroscopy showed disruptions on the graphitic carbon nanotube surface upon both steps. The functionalization extension, measured via TGA mass loss and corroborated via XPS, was 0.2 mmol·g-1. Photophysical studies attest to the presence of the different porphyrin-carbon nanotube connectivity in the nanohybrid. Significantly different emission spectra and fluorescence anisotropy of 0.15-0.3 were observed upon variation of excitation wavelength. Vis-NIR absorption and flash photolysis experiments showed energy/charge transfer in the photoactivated nanohybrid. Moreover, evidence was found for direct reaction of amino groups with a carbon nanotube surface in the presence of molecular dipoles such as the zwitterionic sarcosine amino acid.

Green Aromatic Epoxidation with an Iron Porphyrin Catalyst for One-Pot Functionalization of Renewable Xylene, Quinoline, and Acridine.

Sustainable functionalization of renewable aromatics is a key step to supply our present needs for specialty chemicals and pursuing the transition to a circular, fossil-free economy. In the present work, three typically stable aromatic compounds, representative of products abundantly obtainable from biomass or recycling processes, were functionalized in one-pot oxidation reactions at room temperature, using H2O2 as a green oxidant and ethanol as a green solvent in the presence of a highly electron withdrawing iron porphyrin catalyst. The results show unusual initial epoxidation of the aromatic ring by the green catalytic system. The epoxides were isolated or evolved through rearrangement, ring opening by nucleophiles, and oxidation. Acridine was oxidized to mono- and di-oxides in the peripheral ring: 1:2-epoxy-1,2-dihydroacridine and anti-1:2,3:4-diepoxy-1,2,3,4-tetrahydroacridine, with TON of 285. o-Xylene was oxidized to 4-hydroxy-3,4-dimethylcyclohexa-2,5-dienone, an attractive building block for synthesis, and 3,4-dimethylphenol as an intermediate, with TON of 237. Quinoline was directly functionalized to 4-quinolone or 3-substituted-4-quinolones (3-ethoxy-4-quinolone or 3-hydroxy-4-quinolone) and corresponding hydroxy-tautomers, with TON of 61.

Evaluation of Rhodamine B Photocatalytic Degradation over BaTiO3-MnO2 Ceramic Materials.

Ferroelectric ceramics (BaTiO3_MnO2) with different Mn admixtures were prepared using solid-state synthesis. Elemental analysis, powder X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectroscopy, and impedance spectroscopy confirmed that the BaTiO3 and MnO2 coexisted in the ceramics. In addition, the high purity and homogeneity of the element distributions in the ceramic samples were confirmed. The adsorptive and photocatalytic properties of the BaTiO3 (reference sample, BTO) and BaTiO3_MnO2 materials (BTO_x, where x is wt.% of MnO2 and x = 1, 2 or 3, denoted as BTO_1, BTO_2 and BTO_3, respectively) were evaluated using Rhodamine B (RhB) as the model dye in a photocatalytic chamber equipped with a UV lamp (15 W) in the absence of additional oxidants and (co)catalysts. No adsorption of RhB dye was found for all the materials during 360 min (dark experiment). All samples were photocatalytically active, and the best results were observed for the BTO_3 material, where RhB was 70% removed from aqueous solution during 360 min of irradiation. The photodegradation of RhB in the presence of MnO2-modified BTO ceramics followed a pseudo-first order model and the rate constant of BTO_3 was about 10 times higher than that of BTO, 2 times that of BTO_2, and 1.5 times that of BTO_1. The photocatalysts could be successfully reused after thermal activation.

Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H2TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H2TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

Progress in the Raman spectra analysis of covalently functionalized multiwalled carbon nanotubes: unraveling disorder in graphitic materials.

Raman spectroscopy is highly sensitive to the morphology and electronic structures of graphitic materials, but a convenient interpretation model has been lacking for multiwalled carbon nanotubes (MWCNTs), in particular for the discrimination of spectral changes induced by covalent functionalization. The present work describes a systematic investigation of the Raman analysis of covalently functionalized MWCNTs by diazonium chemistry and oxidation methodologies, with typically different mechanisms and reaction sites. A multi-peak deconvolution system and spectral band assignment were proposed based on the chemical and structural modifications identified by X-ray photoelectron spectroscopy, thermogravimetry, X-ray diffraction, specific surface areas and the comparative analysis of the first and second order regions of the Raman spectra. Diazonium functionalization takes place mainly in the π-system of the external sidewall, while oxidation occurs on defects and leads to structure burning. This allowed us to distinguish between spectral features related to aromaticity disruptions within the sidewalls and spectral features related to changes within the inner tubes. The model was validated extending the studies to the functionalization of MWCNTs by the Bingel reaction.

Biomimetic one-pot route to acridine epoxides.

The first direct epoxidation of acridine on the edge positions is reported. The reaction proceeds under mild conditions using a biomimetic catalytic system based on a Mn(III) porphyrin. The successive oxyfunctionalization to mono-, di-, and tetraepoxy derivatives is accomplished using hydrogen peroxide as a green oxidant at room temperature. Computed optimized geometries showed only slight shifts to the base planarity upon dearomatization by epoxidation, which is an important feature for DNA intercalation and bioactivity. NMR studies and comparison with theoretical values allowed the assignment of the stereochemistry of the anti- and syn-diepoxy and -tetraepoxy derivatives as well as compounds resulting from epoxide ring opening, exemplified by epoxydiol. The diepoxide is formed in an anti:syn ratio of ∼4, and the attack by nucleophiles, exemplified by ethylaniline, occurs selectively and with full conversion, using a microwave process with acetonitrile reflux for 10 min. Finally, studies of the electrostatic potential allowed the mechanisms of the formation of 4-hydroxyacridine and the regioselective reaction of diepoxyacridine with nucleophiles to be rationalized.

An efficient approach for aromatic epoxidation using hydrogen peroxide and Mn(III) porphyrins.

Efficient epoxidation, in very high conversions and selectivities, of aromatic hydrocarbons with hydrogen peroxide, in the presence of Mn(III) porphyrins [Mn(TDCPP)Cl, Mn(beta NO(2)TDCPP)Cl, Mn(TPFPP)Cl] as catalysts is described; naphthalene and anthracene afford the anti-1,2:3,4-arene dioxides whereas with phenanthrene the 9,10-oxide is obtained.

Ion-selective electrodes based on metalloporphyrins for gibberellic acid determination in agricultural products.

This work describes the construction, evaluation and analytical application of electrodes selective to the gibberellate anion for the determination of gibberellic acid in agricultural products. Several types of PVC membrane electrodes without internal reference solution were prepared using the manganese(III) complex of meso-tetraphenylporphyrin (TPP) as ionophore and dibutyl phthalate (DBP), as plasticizer. The incorporation of lipophilic chemical species as additives, was also carried out aiming the evaluation of the response characteristics of the electrodes. To accomplish the analysis of commercial agricultural products a selective membrane composed of 28.0% (w/w) of PVC, 66.0% (w/w) of plasticizer and 6% (w/w) of ionophore was used, with no additive. This potentiometric unit presented a linear response between 10(-4) and 10(-1) mol L(-1) in gibberellate, a slope of about -69 mV dec(-1) and a reproducibility of about +/-1 mV day(-1). The potentiometric analysis of gibberellic acid in commercial products was carried out by direct potentiometry and the results obtained were compared with those provided by HPLC.