The synthesis and photophysicochemical behaviour of novel water-soluble cationic indium(III) phthalocyanine

The syntheses and characterization of 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) and quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) are described. The ground state electronic absorption spectra, photophysics and photochemistry of both dyes in DMSO as well as that of the quaternized compound in aqueous solution are also presented. A comparison of the photophysical and photochemical parameters of the two dyes revealed that quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) was a better photosensitizer than its unquaternized counterpart. The quantum yield values of fluorescence (Φ_F), triplet state formation (Φ_T) and singlet oxygen formation (Φ_Δ) for the cationic dye were found to be 0.03, 0.68 and 0.66 respectively in DMSO; these values were higher than those for 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III), which exhibited values of 0.02, 0.66 and 0.63, respectively in DMSO. The values for the cationic dye in aq. solution were 0.02, 0.59 and 0.56 respectively, suggesting that the water-soluble quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) offers potential as a photosensitizer in photodynamic therapy treatment.     

Characterization of polymeric film of a new manganese phthalocyanine complex octa-substituted with 2-diethylaminoethanethiol, and its use for the electrochemical detection of bentazon

Manganese acetate octakis-(2-diethyaminoethanethiol) phthalocyanine (AcMnODEAETPc) was newly synthesized and characterized by spectroscopic and electrochemical methods. Solution electrochemistry of the complex showed three redox processes assigned to Mn^IIIPc⁻¹/Mn^IIIPc⁻², Mn^IIIPc⁻²/Mn^IIPc⁻² and Mn^IIPc⁻²/Mn^IIPc⁻³ species. The new molecule was polymerized onto a glassy carbon electrode (GCE) to form thin films of different thickness, giving poly-10-AcMnODEAETPc-GCE, poly-20-AcMnODEAETPc-GCE and poly-30-AcMnODEAETPc-GCE, where 10, 20 and 30 represent the number of voltammetry scans during polymerization. Three distinct redox processes were observed on the modified electrode in 0.1 M phosphate buffer solution, pH 5, which confirmed the formation of the polymer. The current signal due to the herbicide, bentazon, was dependent on film thickness; the best signal was obtained on poly-20-AcMnODEAETPc-GCE while poly-10-AcMnODEAETPc-GCE gave the least signal. However, the signals due to the herbicide were better on the different films compared to the bare electrode. Electrochemical impedance spectroscopy (EIS) technique revealed that differences in film thickness offered different charge transfer resistances, R_ct, hence difference in current signals for bentazon oxidation were observed on these films. A Tafel slope of 77 mV/decade, obtained for the herbicide on poly-20-AcMnODEAETPc-GCE, denotes a fast one electron transfer followed by a slow chemical step in the electro-oxidation of bentazon. The voltammetry signals of the herbicide on the films indicated the likely involvement of ring-based redox processes in the detection of the herbicide. A plot of background corrected current response, on this film, versus the concentration of bentazon was linear within the range 50–750 μM with a detection limit of 2.48 × 10⁻⁷ M.     

Metallophthalocyanine catalysed electroreduction of nitrate and nitrite ions in alkaline media

The electrochemical reduction of nitrite and nitrate in alkaline solution has been studied on glassy carbon electrodes modified with phthalocyanine complexes of Mn, Fe, Co, Ni, Cu and Zn (MnPc, FePc, CoPc, NiPc, CuPc and ZnPc, respectively, and Pc(-2) is phthalocyanine dianion). Voltammetry shows that the reduction of nitrite occurs at potentials slightly less negative than for nitrate reduction. The MPc complexes lower the overpotential for the reduction of nitrite and nitrate as follows: CuPc > FePc > NiPc > CoPc > MnPc > ZnPc > glassy carbon electrode. The main product for the reduction of nitrite and nitrate is ammonia, with high yields of ammonia being obtained, depending on the choices of the electrolysis potential and MPc complex.     

Synthesis,photophysics, photochemistry and fluorescence quenching studies on highly soluble substituted oxo-titanium(IV) phthalocyanine complexes

The synthesis, photophysical and photochemical properties of soluble 3,4-(methylendioxy)-phenoxy substituted oxo-titanium(IV) phthalocyanines (4–6) are reported for the first time. The new compounds have been characterized by elemental analysis, FT-IR, ¹H NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for fluorescence lifetimes and fluorescence, photodegradation and singlet oxygen quantum yields, of these compounds in dimethylsulfoxide (DMSO) and toluene. The effects of the position of the substituents and solvent effect on the photophysical and photochemical parameters of the oxo-titanium(IV) phthalocyanines (4–6) are also reported. The fluorescence of the substituted oxo-titanium(IV) phthalocyanine complexes (4–6) is effectively quenched by 1,4-benzoquinone (BQ) in both DMSO and toluene.     

Tuning the redox properties of Co-N4 macrocyclic complexes for the catalytic electrooxidation of glucose

Graphite electrodes modified with four different cobalt N4 macrocyclics, namely Co tetrapentapyridinophthalocyanine, (CoTPenPyrPc), Co tetrapyridinoporphyrazine (CoTPyPz), Co octa(hydroxyethylthio)phthalocyanine (CoOEHTPc) and Co tetranitrophthalocyanine (CoTNPc) exhibit catalytic activity for the oxidation of glucose in alkaline media. The purpose of this work is to establish correlations between the catalytic activity of these complexes and their redox potential. The activity of the different modified electrodes was tested by linear voltammetry under hydrodynamic conditions using the rotating disk technique. Tafel plots constructed from mass-transport corrected currents give slopes ranging from 0.080 to 0.160 V/decade for the different catalysts which suggests that a first one-electron step is rate controlling with the symmetry of the energy barrier depending on the nature of the ligand of the Co complex. A plot of log I versus the Co(II)/(I) formal potential gives a volcano curve that also includes catalysts studied previously. This illustrates the concept that the formal potential of the catalyst needs to be tuned to a certain value for achieving maximum activity. A theoretical interpretation of these results is given in terms of Langmuir isotherms for the adsorption of glucose on the Co sites of the surface-confined metal complexes.     

Catalytic oxidation of thioanisole using oxovanadium(IV)‐functionalized electrospun polybenzimidazole nanofibers

Polybenzimidazole fibers, with an average diameter of 262 nm, were produced by the process of electrospinning. These fibers were used as a solid support material for the immobilization of oxovanadium(IV) which was achieved via a reaction with vanadyl sulfate. The oxovanadium(IV)‐functionalized nanofibers were used as heterogeneous catalysts for the oxidation of thioanisole under both batch and pseudo‐continuous flow conditions with great success. Under batch conditions near quantitative oxidation of thioanisole was achieved in under 90 min, even after four successive catalytic reactions. Under continuous conditions, excellent conversion of thioanisole was maintained throughout the period studied at flow rates of up to 2 mLh^?1. This study, therefore, proposes that electrospun polybenzimidazole nanofibers, with their small diameters, impressive chemical and thermal stability, as well as coordinating benzimidazole group, may be a desirable support material for immobilization of homogeneous catalysts. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characterization of manganese tetraarylthiosubstituted phthalocyanines self assembled monolayers

Manganese tetraarylthiosubstituted phthalocyanines (complexes 1-5) have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. SAM characteristics reported in this work are: ion barrier factor (∼1); interfacial capacitance (303-539 μF cm⁻²) and surface coverage (1.06 × 10⁻¹⁰-2.80 × 10⁻¹⁰ mol cm⁻²). Atomic force microscopy was employed in characterizing a SAM. SAMs of complexes 1-5 were employed to detect l-cysteine (with limit of detection ranging from 2.83 × 10⁻⁷ to 3.14 × 10⁻⁷ M at potentials of 0.68-0.75 V vs. Ag|AgCl) and nitrite (limit of detection ranging from 1.78 × 10⁻⁷ to 3.02 × 10⁻⁷ M at potentials of 0.69-0.76 V vs. Ag|AgCl).     

Insights into the surface and redox properties of single-walled carbon nanotube—cobalt(II) tetra-aminophthalocyanine self-assembled on gold electrode

This paper describes for the first time the electrochemical properties of redox-active self-assembled films of single-walled carbon nanotubes (SWCNTs) coordinated to cobalt(II)tetra-aminophthalocyanine (CoTAPc) by sequential self-assembly onto a preformed aminoethanethiol (AET) self-assembled monolayer (SAM) on a gold electrode. Both redox-active SAMs (Au-AET-SWCNT and Au-AET-SWCNT-CoTAPc) exhibited reversible electrochemistry in aqueous (phosphate buffer) solution. X-ray photoelectron spectroscopy (XPS) confirmed the appearance on the gold surface of the various elements found on the SAMs. Atomic force microscopy (AFM) images prove, corroborating the estimated electrochemical surface concentrations, that these SAMs lie normal to the gold surface. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)₆]^3−/4− as a redox probe revealed that the Au-AET-SWCNT-CoTAPc showed much lower (∼10 times) electron-transfer resistance (R_et) and much higher (∼10 times) apparent electron-transfer rate constant (k_app) compared to the Au-AET-SWCNT SAM. Interestingly, a preliminary electrocatalytic investigation showed that both SAMs exhibit comparable electrocatalytic responses towards the detection of dopamine in pH 7.4 phosphate buffer solutions (PBS). The electrochemical studies (cyclic voltammetry (CV) and EIS) prove that SWCNT greatly improves the electronic communication between CoTAPc and the Au electrode surface.     

Optimal and energy efficient operation of conveyor belt systems with downhill conveyors

Downhill conveyors are important potential energy sources within conveyor belt systems (CBSs). Their energy can be captured using regenerative drives. This paper presents a generic optimisation model for the energy management of CBSs that have downhill conveyors. The optimisation model is able to optimally schedule three configurations of a case-study CBS that is connected to the grid and operated under a time-of-use tariff. The three suggested drive configurations showcase potential energy savings/incomes that can be obtained from implementing: (a) variable speed control, (b) internal use of downhill conveyor energy and (c) the export of energy to the grid. The results show that a CBS with a daily energy consumption of 924 kWh can be reconfigured and controlled to reduce consumption by 53 or 100 % or be made to generate 1984 kWh, depending on the configuration. Analysis of the investment in each of the three configurations is assessed using a life-cycle cost and payback period (PBP). The daily operation simulation results show that the use of regenerative drives and variable speed control is able to provide energy savings in CBSs. The cost analysis shows that the configuration that enables sale of energy to the grid is the most profitable arrangement, for the case study plant under consideration. The sensitivity analysis indicates that the PBPs are more sensitive to the annual electricity price increases than changes in the discount rate. Combining regenerative drives and optimal operation of CBS generates energy savings that give attractive PBPs of less than 5 years.     

The synthesis and fluorescence behaviour of new unsymmetrically mono-functionalized carboxy Ge, Ti and Sn phthalocynines

This work reports on the synthesis and fluorescence behaviour of novel unsymmetrically substituted monocarboxy germanium ((OH)₂GeMCPc, 3), titanium (OTiMCPc 4) and tin ((ac)₂SnMCPc, 5) phthalocyanines. The fluorescence quantum yields ranged from 0.09 to 0.14. The fluorescence lifetimes were found to be higher for the complex with higher fluorescence quantum yield value. Higher fluorescence quantum yields and lifetimes were obtained for the (ac)₂SnMCPc complex (5), followed by OTiMCPc complex (4), and the lowest fluorescence quantum yield and lifetime were observed for (OH)₂GeMCPc (3).