Phototransformation of pollutants using lutetium and zinc phthalocyanines anchored on electrospun polymer fibers

Novel lanthanide phthalocyanines containing dysprosium, erbium and lutetium as central metals were synthesized using phthalonitrile:metal salt ratio of 4:1 or lower phthalonitrile content as well as using unmetallated phthalocyanine. They were characterized using various spectroscopic and elemental analyses. Dysprosium bis-phthalocyanine was obtained while monomers were obtained for erbium and lutetium phthalocyanines. Theopen-shelldysprosiumbis-phthalocyanine and the monomeric complex of the open-shell erbium were neither fluorescent nor showed the ability to generate singlet oxygen. The triplet states of all the lutetium phthalocyanines were found to be populated with high triplet quantum yields and corresponding high singlet oxygen quantum yields. The fluorescence quantum yields of the lutetium phthalocyanines were however found to be very low. The lutetium phthalocyanines together with unsubstituted zinc phthalocyanine and its derivatives were successfully incorporated into electrospun polymer fibers either by covalent linkage or sorption forces. Spectral characteristics of the functionalized electrospun polymer fibers indicated that the phthalocyanines were bound and their integrity maintained within the fiber matrices. Most importantly the fluorescence and photoactivity of the phthalocyanines were equally maintained within the electrospun fibers. The functionalized electrospun polymer fibers especially those containing the zinc phthalocyanines could qualitatively detect nitrogen dioxide, a known environmental air pollutant. Also all the functionalized electrospun polystyrene and polysulfone fibers containing lutetium and zinc phthalocyanines could be applied for the photoconversion of 4-chlorophenol, 4-nitrophenol and methyl orange. Those of polystyrene could be re-used. Polyacrylic acid and polyurethane functionalized electrospun fibers were found not to be suitable for photocatalytic applications in aqueous medium. 4-Chlorophenol was found to be more susceptible to photodegradation while methyl orange very difficult to degrade

Comparative phototransformation of environmental pollutants using metallophthalocyanines supported on electrospun polymer fibers

The fluorescence and photoactivity of a series of Zn and Lu phthalocyanine complexes incorporated in various polymer fibers were investigated for the phototransformation of 4-chlorophenol, 4-nitrophenol, and methyl orange. The phthalocyanine complexes functionalized on polystyrene and polysulfone polymer fibers could be applied in the degradation of 4-chlorophenol, 4-nitrophenol, and methyl orange with 4-chlorophenol being much more susceptible to degradation while methyl orange was the least. Also polymer fibers of polystyrene were found to be reusable

Electrospun polyacrylic acid polymer fibers functionalized with metallophthalocyanines for photosensitizing and gas sensing applications

The photophysical and photochemical properties of tetraaminophthalocyanine complexes of lutetium and zinc covalently linked to polyacrylic acid were studied alongside those of unsubstituted zinc phthalocyanine within the same polymeric fiber matrix. All three phthalocyanines within the solid fiber matrices showed photoactivity by the generation of singlet oxygen as was observed in solution. The fluorescence behaviors of the composite fibers equally parallel those in solution. For the unsubstituted zinc phthalocyanine composite, the fiber showed fluorescence quenching on interaction with gaseous nitrogen dioxide similar to that in DMF and, thus could be a promising nanofabric material in developing optoelectronic devices that are responsive to the gas

Photophysical characterization of dysprosium, erbium and lutetium phthalocyanines tetrasubstituted with phenoxy groups at non-peripheral positions

Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01

Photooxidation of 4-chlorophenol sensitized by lutetium tetraphenoxy phthalocyanine anchored on electrospun polystyrene polymer fiber

An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms

A highly selective and sensitive pyridylazo-2-naphthol-poly (acrylic acid) functionalized electrospun nanofiber fluorescence “turn-off” chemosensory system for Ni 2+

A fluorescent nanofiber probe for the determination of Ni2+ was developed via the electrospinning of a covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymer. Fluorescent nanofibers with diameters in the range 230–800 nm were produced with uniformly dispersed fluorophores. The excitation and emission fluorescence were at wavelengths 479 and 557 nm respectively, thereby exhibiting a good Stokes' shift. This Ni2+ probe that employs fluorescence quenching in a solid receptor–fluorophore system exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 μg mL−1 based on the Stern–Volmer mechanism. The probe achieved a detection limit (3δ/S) of 0.07 ng mL−1 and a precision, calculated as a relative standard deviation (RSD) of more than 4% (n = 8). The concentration of Ni2+ in a certified reference material (SEP-3) was found to be 0.8986 μg mL−1, which is significantly comparable with the certified value of 0.8980 μg mL−1. The accuracy of the determinations, expressed as a relative error between the certified and the observed values of certified reference groundwater was ≤0.1%. The versatility of the nanofiber probe was demonstrated by affording simple, rapid and selective detection of Ni2+ in the presence of other competing metal ions by direct analysis, without employing any further sample handling steps

Electrospun polyacrylic acid polymer fibers functionalized with metallophthalocyanines for photosensitizing and gas sensing applications

The photophysical and photochemical properties of tetraaminophthalocyanine complexes of lutetium and zinc covalently linked to polyacrylic acid were studied alongside those of unsubstituted zinc phthalocyanine within the same polymeric fiber matrix. All three phthalocyanines within the solid fiber matrices showed photoactivity by the generation of singlet oxygen as was observed in solution. The fluorescence behaviors of the composite fibers equally parallel those in solution. For the unsubstituted zinc phthalocyanine composite, the fiber showed fluorescence quenching on interaction with gaseous nitrogen dioxide similar to that in DMF and, thus could be a promising nanofabric material in developing optoelectronic devices that are responsive to the gas

Zinc (II) 2, 9, 16, 23-tetrakis [4-(N-methylpyridyloxy)]-phthalocyanine anchored on an electrospun polysulfone polymer fiber: Application for photosensitized conversion of methyl orange

In this work, a comparative study of photodegradation of methyl orange, an azo dye, in homogeneous aqueous solution of a quarternized cationic zinc phthalocyanine and a heterogeneous catalytic system based on the same phthalocyanine anchored on polysulfone polymer fiber is presented. In both cases, conversion involved the azo bond of the dye with no detectable opening up of the aromatic benzene rings. The reaction kinetics in both cases were consistent with first order with the conversion occurring in the homogeneous system being faster than when the functionalized polymer fiber was used. The reaction products consisted of a coupling product as well as a series of oligopolymeric products

Theoretical Study of Terminal Vanadium(V) Chalcogenido Complexes Bearing Chlorido and Methoxido Ligands

Solvent (methanol) coordinated vanadium(V) chalcogenido complexes bearing chlorido and methoxido ligands have been studied computationally by means of density functional (DFT) methods. The gas phase complexes were fully optimized using B3LYP/GEN functionals with 6-31+G⁎⁎ and LANL2DZ basis sets. The optimized complexes show distorted octahedral geometries around the central vanadium atom. The ligand pπ-vanadium dπ interactions were analyzed by natural bond order (NBO) and natural population analyses (NPA). These results show strong stabilization of the V=O bond as was further confirmed by the analyses of the frontier molecular orbitals (FMOs). Second-order perturbation analyses also revealed substantial delocalization of lone pair electrons from the oxido ligand into vacant non-Lewis (Rydberg) orbitals as compared to the sulfido and seleno analogues. These results show significant ligand-to-metal charge transfer (LMCT) interactions. Full interaction map (FIM) of the reference complex confirms hydrogen bond interactions involving the methanol (O-H) and the chlorido ligand

Physico-chemical properties of lutetium phthalocyanine complexes in solution and in solid polystyrene polymer fibers and their application in photoconversion of 4-nitrophenol

The photophysical and photochemical behavior of two phthalocyanine complexes of lutetium peripherally substituted with tetraphenoxy and tetra-2-pyridiloxy groups were studied in solution and when dispersed in polystyrene polymer fiber. The phthalocyanines were found not to fluoresce significantly in solution and not at all within the fiber matrix as compared with standard unsubstituted zinc phthalocyanine. They showed very promising photoactivity in solution with high singlet oxygen quantum yields. Their photoactivity within the polymer fiber matrix was also demonstrated with the photoconversion of 4-nitrophenol, a water pollutant. The photodegradation process with both phthalocyanines follows first order kinetics similar to that observed for the zinc phthalocyanine and the photo-products were found to be hydroquinone, benzoquinone and 4-nitrocatechol