Synthesis, characterization and application of monocarboxy-phthalocyanine-single walled carbon nanotube conjugates in electrocatalysis

In this paper we report on the synthesis, characterization and use of monocarboxy-phthalocyanine-single walled carbon nanotube conjugates in the electrocatalysis of amitrole and diuron. UV-Vis, FTIR and XRD spectroscopies were used in the characterization of cobalt(II)-tris(benzyl-mercapto)-mono(carboxyphenoxy)-phthalocyanine conjugates (CoMCPc-PA-SWCNT(linked)), while AFM was used to show changes in surface morphologies of the modified electrodes. Cyclic voltammetry and chronoamperometry were used for the electrocatalytic oxidation of amitrole and diuron on the modified glassy carbon electrode. The catalytic rate constants for amitrole and diuron were found to be 1.83 × 10⁶ and 1.99 × 10⁶ M⁻¹ s⁻¹, respectively. The linear range for both was 1.0 × 10⁻⁵-2.0 × 10⁻⁴ M, with sensitivities of 5.10 and 3.70 A mol⁻¹ L cm⁻² for amitrole and diuron, respectively. The limits of detection were estimated to be 0.14 and 0.20 μM for amitrole and diuron, respectively, using the 3δ notation.     

Electrode Modification Using Alkynyl Substituted Fe(II) Phthalocyanine via Electrografting and Click Chemistry for Electrocatalysis

In this work, tetrakis(5‐hexyn‐oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4‐azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne‐azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM^?1 and a limit of detection of 1.09 µM.     

Synthesis, characterization, and photophysical properties of novel ball-type dinuclear and mononuclear containing four 1,1'-binaphthyl-8,8'-diol bridged metallophthalocyanines with long triplet state lifetimes

The syntheses of new ball-type dinuclear Si(IV)(CH(3)COO)(2) and Ti(IV)O phthalocyanines and two different mononuclear Zn(II) and Ti(IV)O phthalocyanines containing four 1,1'-binaphthyl-8,8'-diol substituents on the peripheral positions are described. The structures of these compounds were characterized using the elemental analyzes, UV-Vis, FT-IR, (1)H NMR and mass spectroscopies. The Φ(F) values are 0.14, 0.10, 0.04, 0.02, 0.07; Φ(T) values are 0.69, 0.71, 0.85, 0.33, 0.71 for 7-11, respectively. All complexes showed very long triplet lifetimes with τ(T) 7510, 3190, 2880, 2370, 9470 μs for 7-11 in DMSO, respectively.     

Electrochemical, microscopic and spectroscopic characterization of benzene diamine functionalized single walled carbon nanotube-cobalt (II) tetracarboxy-phthalocyanine conjugates

In this paper we report on the synthesis and characterization of 1,4-benzene diamine (BDA) functionalized single walled carbon nanotubes linked to cobalt (II) tetracarboxy-phthalocyanine. The characterization of the conjugate was through UV-vis, FTIR and X-ray diffraction (XRD) spectroscopies and by transmission electron microscope (TEM) and electrochemical methods. The conjugate is used for the electrochemical characterization of diuron. The catalytic rate constant for diuron was 4.4×10(3)M(-1)s(-1) and the apparent electron transfer rate constant was 18.5×10(-6)cms(-1). The linear dynamic range was 1.0×10(-5)-2.0×10(-4)M, with a sensitivity of ～0.42Amol(-1)Lcm(-2) and a limit of detection of 0.18μM using the 3δ notation.     

Synthesis and electrochemical characterisation of a near infrared absorbing oxo vanadium(IV) octapentylthio-phthalocyanine

The synthesis of an α-substituted phthalocyanine oxo vanadium(IV) 1,4,8,11,15,18,22,25-octapentathiophthalocyanine (4) which absorbs at 850 nm in dichloromethane is reported. The complex is purple in colour and becomes green on reduction. The cyclic and square wave voltammetries of the complex show five redox couples. The spectroelectrochemical data showed only ring based processes. The ring reduced species is observed at wavelengths greater than 680 nm rather than the usual 500–600 nm range typical of ring reduced phthalocyanine complexes.     

Electrocatalytic Activity of Nanocomposites of Sulphur Doped Graphene Oxide and Nanosized Cobalt Phthalocyanines

In this work we explore the electrocatalytic activity of nanocomposites of reduced sulphur doped graphene oxide nanosheets (rSDGONS) and cobalt phthalocyanine (CoPc) or cobalt tetra amino phthalocyanine (CoTAPc) towards hydrogen peroxide. Transmission electron microscopy, scanning electron microscopy, X‐ray photon spectroscopy, X‐ray diffraction, chronoamperometry, linear scan voltammetry and cyclic voltammetry were used to characterize the nanocomposites. Nanosized CoPc showed superior (in terms of currents) electrocatalytic oxidation and reduction of hydrogen peroxide compared to CoTAPc nanoparticles (CoTAPc NP ). The lowest detection limit was obtained for hydrogen peroxide oxidation on electrodes modified with CoPc NP ‐rSDGONS at 1.49 µM. The same electrode gave a high adsorption equilibrium constant of 1.27×10³ mol^?1 and a Gibbs free energy of ?17.71 kJ/mol, indicative of a spontaneous reaction on the electrode surface.     

Characterization and Electrocatalytic Activity of Nanocomposites Consisting of Nanosized Cobalt Tetraaminophenoxy Phthalocyanine,Multi‐walled Carbon Nanotubes and Gold Nanoparticles

Glassy carbon electrodes were modified with composites containing cobalt tetraaminophenoxy phthalocyanine nanoparticles (CoTAPhPc NP ), multi‐walled carbon nanotubes (MWCNT) and gold nanorods (AuNRs). The modified electrodes were studied for their electrocatalytic behavior towards the reduction of hydrogen peroxide. Phthalocyanine nanoparticles significantly improved electron transfer kinetics as compared to phthalocyanines which are not in the nanoparticle form when alone or in the presence of multiwalled carbon nanotubes (MWCNTs). CoTAPhPc NP ‐MWCNT‐GCE proved to be suitable for hydrogen peroxide detection with a catalytic rate constant of 3.45×10³ M^?1 s^?1 and a detection limit of 1.61×10^?7 M. Adsorption Gibbs free energy ΔG^o was found to be ?19.22 kJ mol^?1 for CoTAPhPc NP ‐MWCNT‐GCE.     

Synthesis, spectroscopic and electrochemical properties of manganese, nickel and iron octakis-(2-diethylaminoethanethiol)-phthalocyanine

The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the Mn^IIIPc⁻²/Mn^IIPc⁻² (E_½ = −0.12 V versus Ag|AgCl) and Mn^IIPc⁻²/Mn^IIPc⁻³ (E_½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the Fe^IIPc⁻²/Fe^IPc⁻² (E_½ = −0.35 V versus Ag|AgCl) and Fe^IPc⁻²/Fe^IPc⁻³ (E_½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to Fe^IIIPc⁻²/Fe^IIPc⁻² (E_½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.     

Photophysical,photochemical and electrochemical properties of water soluble silicon,titanium and zinc phthalocyanines

The photophysical, and photochemical properties of titanium, silicon and zinc octacarboxy phthalocyanine (OTiOCPc, (OH)₂SiOCPc and ZnOCPc) and their tetrasulfonated counterparts (OTiTSPc, (OH)₂SiTSPc and ZnTSPc) in phosphate-buffer solution (PBS), pH 10 were studied. The tetrasulfonated derivatives were also studied in the presence of a surfactant, cremophore EL (CEL) due to their high aggregation tendency in aqueous solutions. Triplet quantum yields ranged from 0.20 to 0.48 for MOCPcs and 0.32–0.65 for MTSPcs in the presence of CEL and in pH 10. High triplet lifetimes were observed for ZnTSPc (270 μs, in the presence of CEL) or ZnOCPc (130 μs) compared to values ranging from 50 to 70 μs for the rest of the complexes.     

Metallophthalocyanine Based Carbon Paste Electrodes for the Determination of 2′,3′‐Dideoxyinosine

Novel electrochemical sensors based on carbon paste impregnated with metallopthalocyanine (MPc, M=Co, Fe) complexes, have been constructed for the assay of anti‐HIV drug 2′,3′‐dideoxyinosine (didanosine, DDI). Both modified electrodes showed electrocatalytic activity towards the oxidation of dideoxyinosine in phosphate buffer pH 7.4 with a working concentration range of 10^?6–10^?4 mol/L and a detection limit of 10^?7 mol/L magnitude order. The sensor proved to be highly reliable for the assay of the purity of DDI ‐ raw material as well as for the uniformity content test of Videx tablets.