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In this work, we present Zn, CoII, and MnIII metalated meso‐tetra‐[4‐(methylthio) phenyl] porphyrin ([Zn(TMtPP)], [CoII(TMtPP], and [MnIII(TMtPP)Cl]) as electrocatalysts and photoelectrocatalysts for electrochemical detection and photoelectrocatalytic degradation of pentachlorophenol (PCP). The complexes were characterized using UV‐visible spectroscopy, mass spectroscopy, and elemental analysis. Proton nuclear magnetic resonance (1H NMR) studies were only conducted for the Zn derivative. The electrochemical detection of PCP was carried out using cyclic voltammetry and chronoamperometry. [CoII(TMtPP)] showed better detection limit. For photoelectrocatalytic (PEC) degradation studies of PCP, linear sweep voltammetry and UV‐visible spectra were employed. [Zn(TMtPP)] showed better removal efficiency. The main species responsible for the PEC degradation were found to be superoxide radicals (⋅O2) and electron holes (h+). [ABSTRACT FROM AUTHOR]

We report on the effect of detonation nanodiamonds (DNDs) on electrocatalytic properties of an asymmetrically substituted cobalt phthalocyanine (CoPc). The incorporation of DNDs onto cobalt phthalocyanine enhances its electrochemical behaviour. An asymmetrical CoPc alone, when π‐π stacked (CoPc‐DNDs(ππ)) or covalently linked (CoPc@DNDs) to DNDs is used to modify a glassy carbon electrode (GCE) for the electrocatalytic detection of hydrazine. In addition, the GCE was modified by sequentially adding CoPc and DNDs onto its surface, represented as GCE/CoPc‐DNDs(seq) when CoPc is placed before DNDs on the electrode and GCE/DNDs‐CoPc(seq) when DNDs are placed before CoPc, where seq represents sequential. The obtained catalytic rate for the detection of hydrazine on GCE/CoPc@DNDs was 9.3×104 M−1.s−1 with a limit of detection as 0.33 μM. GCE/CoPc@DNDs gave better electrocatalytic activities when compared to its counterparts. [ABSTRACT FROM AUTHOR]

Manganese and cobalt metalated 5, 10, 15‐tris(aminophenyl)‐20‐(4‐carboxyphenyl) porphyrins (ClMnTA3CPP and CoTA3CPP) were synthesized and attached to graphene quantum dots (GQDs) via π‐π interaction and electrostatic interaction. The electrochemical oxidation of hydrazine was performed via cyclic voltammetry and chronoamperometry. The CoTA3CPP showed good electrocatalytic activity towards the oxidation of hydrazine in terms of catalytic rate constants and limits of detection (LoD). ClMnTA3CPP showed lower overpotential 0.60 V. The introduction of GQDs improved the electrocatalytic ability when combined with CoTA3CPP and ClMnTA3CPP with the lowest LoD (0.0025 mM CoTA3CPP–GQDs) followed by ClMnTA3CPP–GQDs with 0.0033 mM. [ABSTRACT FROM AUTHOR]

This paper explores the synthesis and characterisation of an asymmetrical Co phthalocyanine (CoPc), and its covalent linking to two tungsten nanoparticles: bismuth tungsten oxide (Bi2WO6) and nickel tungsten oxide (NiWO4). The nanoparticles were also mixed with the CoPc. The CoPc, nanoparticles and their respective conjugates were used as electrocatalysts in the electrochemical detection of nitrite. The electrocatalysts studied in this work had sensitivities ranging from 3–133 μA/mM while the limits of detection (LoDs) ranged between 0.063 μM and 1.7 μM. Bi2WO6 and its conjugate exhibited better LoD than corresponding NiWO4 and conjugate. [ABSTRACT FROM AUTHOR]

Glass carbon electrodes (GCE) were modified with metal organic frameworks (MOFs) containing molybdenum polyoxometallates (Mo POMs) in a copper benzene tricarboxylate framework (HKUST-1). The Mo POMs were introduced via one-pot synthesis (Mo2) and post-synthetic modification (Mo1) techniques. The electrode modifiers were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermal analysis. The modified electrodes' oxidation capacity toward l-cysteine was studied. Mo POMs significantly improved electron transfer kinetics compared to the bare GCE. The best Mo POM doped electrode (Mo1-GCE) had a catalytic rate constant of 2.2 × 104 M−1 s−1 and a limit of detection of 3.07 × 10−7 M. Under the employed experimental conditions, the detection response for l-cysteine was very fast (within 0.1 s) for all the modified electrodes and selective toward l-cysteine in the presence of other amino acids. [ABSTRACT FROM AUTHOR]

A symmetrical cardanol‐based cobalt phthalocyanine (Pc) along with its asymmetrical acid‐based derivatives were synthesized and applied in the electrocatalysis of hydrazine. Despite the inhibition of electron movement by the bulky cardanol‐based substituent throughout the series of molecules, an ideal combination of substituents was established in GCE‐3 (2,9,16‐tris(3‐pentadecylphenoxy)‐23‐mono propionic acid phthalocyanato cobalt (II)) where a limit of detection (LoD) value of 5.10 μM (signal to noise ratio=5) was recorded for the detection of hydrazine. The results obtained serve as an illustration that the combination of electron‐donating and electron‐withdrawing substituents has a significant influence on the complete functioning of the phthalocyanine molecule(s) being investigated. [ABSTRACT FROM AUTHOR]

Paracetamol (PA), being an analgesic and antipyretic medicine, can cause fatal hepatotoxicity and nephrotoxicity when overdosed. It is therefore important to develop electrochemical sensors that can monitor and quantify it in aquatic environments. In this study, rare‐earth sandwich‐type phthalocyaninato chelates based on neodymium (1 a) and samarium (1 b) were employed as electrocatalysts to modify glassy carbon electrodes (GCE) for the first time. It was found that 1 a‐modified GCE (herein referred to as 1 a‐GCE) is less conductive than 1 b‐modified counterpart (1 b‐GCE). A larger rate constant was also obtained for 1 b‐GCE. It was established that a faster oxidation rate efficiency was responsible for lower limit of detection value obtained for 1 b‐GCE as compared to 1 a‐GCE. [ABSTRACT FROM AUTHOR]

Glassy carbon electrodes or plates were modified with nanocomposites consisting of cobalt tetraaminophenoxyphthalocyanine (CoTAPhPc), reduced graphene oxide nanosheets (rGONs) and multi-walled carbon nanotubes (MWCNTs). The modified electrodes were characterized using cyclic voltammetry, scanning electrochemical microscopy (SECM) and time-of-flight-secondary ion mass spectrometer (TOF-SIMS). The electrocatalytic activity of the modified electrode was tested for detection of L-cysteine. The presence of CoTAPhPc on sequential layers of MWCNT and rGONs resulted in improved detection currents compared to CoTAPhPc alone or when MWCNT/rGONs are mixed in CoTAPhPc–MWCNT/rGONs (mix)–glassy carbon electrode (GCE). CoTAPhPc–MWCNT–GCE (without rGONS) showed higher sensitivity toward l-cysteine as compared to the probes incorporating rGONs with a catalytic rate constant of 4.62 × 104 M−1s−1 and a detection limit of 30 nM. The presence of rGONs improved the stability of the electrode. [ABSTRACT FROM AUTHOR]

Abstract This work describes the conjugation of Co, Mn and Fe tetra ethynyl benzyl phthalocyanines to CdTe/ZnS quantum dots via click chemistry. The synthesized conjugates were then immobilised on glassy carbon electrode and their electrocatalytic activity towards hydrogen peroxide oxidation and oxygen reduction investigated. CoPc(1)-QDs showed superior electrocatalytic behaviour towards hydrogen peroxide catalysis with sensitivity of 2.8 × 105 μA/mM and limit of detection of 0.023 μM. On the other hand, FePc(3)-QDs showed the best oxygen reduction activity involving a direct 4-electron mechanism. Highlights • Co, Mn and Fe tetra ethynyl benzyl phthalocyanines are conjugated to CdTe/ZnS quantum dots via click chemistry. • The conjugates are immobilised on glassy carbon electrode for detection of hydrogen peroxide and oxygen. • The CoPc derivative showed superior electrocatalytic behaviour towards hydrogen peroxide catalysis. • The FePc derivative showed the best oxygen reduction activity involving a direct 4-electron mechanism. [ABSTRACT FROM AUTHOR]

A series of Co phthalocyanine (CoPc) derivatives and their respective nitrogen doped graphene quantum dot conjugates were used as catalysts towards the electrooxidation of hydrazine. Using a glassy carbon electrode as a support for the electrocatalysts, through cyclic voltammetry and chronoamperometry, the effects of combining the CoPcs with the nitrogen doped graphene quantum dots (NGQDs) were studied. The general observations made were that the NGQDs improve the catalytic activity of the CoPcs in both the π‐π stacked and covalently linked conjugates by increasing the sensitivities and lowering the limits of detection with values as low as 0.43 μM being recorded. [ABSTRACT FROM AUTHOR]

In this work, we report on the synthesis and applications of a new cobalt tetrakis 4-((4-ethynylbenzyl) oxy) phthalocyanine (3) for the detection of hydrazine. The glassy carbon electrode (GCE) was first grafted through diazotization, providing the GCE surface layer with azide groups. Thereafter, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper(I) catalyst was used to “click” complex 3 to the grafted surface of GCE. The new platform was then characterized using cyclic voltammetry (CV), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). This work shows that 3 is an effective sensor with sensitivity of 91.5 μA mM−1 and limit of detection of 3.28 μM which is a great improvement compared to other reported sensors for this analyte. [ABSTRACT FROM AUTHOR]

Tetracarboxyphenoxy phthalocyanine was covalently linked to multi-walled carbon nanotubes and the conjugate was used for modification of glassy carbon electrodes for the detection of hydrogen peroxide. The electrocatalytic behavior was examined by cyclic voltammetry, square wave voltammetry, and rotating disk electrode. The results show that covalent linking is attractive in terms of high detecting currents, low overpotential, and high catalytic rate constants. Very low detection limits were observed with CoTCPhPc-DAMN-MWCNT(linked)-GCE at 0.33 nM. The resulting catalytic rate constant was 1.1 × 103 M−1s−1. [ABSTRACT FROM PUBLISHER]

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 (CoTAPcNP). The lowest detection limit was obtained for hydrogen peroxide oxidation on electrodes modified with CoPcNPrSDGONS at 1.49 mM. 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. [ABSTRACT FROM AUTHOR]

In this work, azidobenzene diazonium salt is grafted onto a glassy carbon electrode (GCE) followed by clicking of manganese tetrahexynyl phthalocyanine for the electrocatalysis of hydrazine. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper catalyst was utilized to RclickQ the manganese tetrahexynyl phthalocyanine to the surface of the grafted GCE. This new platform was then characterized using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and X-ray photoelectron spectroscopy (XPS). Based on the cyclic voltammetry calibration curve of electrocatalysis for hydrazine, the clicked Mn phthalocyanine electrode proved to be an effective sensor with a sensitivity of 27.38 μA mM-1 and the limit of detection (LoD) of 15.4 pM which is a great improvement compared to other reported sensors for this analyte. [ABSTRACT FROM AUTHOR]

Conjugates of reduced phosphorus-nitrogen co-doped graphene oxide nanosheets (rPNDGONS), reduced phosphorus doped graphene oxide nanosheets (rPDGONS), reduced nitrogen doped graphene oxide nanosheets (rNDGONS), reduced pyrolised graphene oxide nanosheets (rpyGONS) with nanosized cobalt (II) phthalocyanine (CoPc NP ) or cobalt tetra amino phenoxy phthalocyanine (CoTAPhPc NP ) were characterised and tested for their electrocatalytic behaviour towards the detection of hydrogen peroxide. Cyclic and linear scan voltammetries, and chronoamperometry were used to evaluate the electrocatalytic nature of the designed probes. For hydrogen peroxide detection, CoPc NP -rPNDGONS-GCE oxidation gave sensitivity of 12.00 mA/M, limit of detection of 4.48 nM, a rate constant of 2.66 × 10 5 M −1 s −1 , adsorption equilibrium constant of 3.7 × 10 2 M −1 and Gibbs free energy −14.84 kJmol −1 . The lowest detection limit was obtained for CoTAPhPc NP -rPNDGONS-GCE at 1.21 nM. [ABSTRACT FROM AUTHOR]

Reduced graphene oxide nanosheets (rGONS), reduced boron doped graphene oxide nanosheets (rBDGONS) and reduced nitrogen doped graphene oxide nanosheets (rNDGONS) and their composites with cobalt tetra aminophenoxy phthalocyanine nanoparticles (CoTAPhPc NP) were employed towards the detection of hydrogen peroxide. The nanomaterials were characterized by absorption spectroscopy, transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, linear sweep voltammetry and cyclic voltammetry. rNDGONS showed excellent electrooxidation and electroreduction of hydrogen peroxide supported by superior surface coverage values. The inclusion of nanosized Pc significantly lowered the reduction overpotential. CoTAPhPc NP -rNDGONS-GCE gave a sensitivity of 39.30 mA/M, catalytic rate constant of 1 × 10 3 M −1 s −1 and a detection limit of 8.2 nM. An adsorption equilibrium constant and Gibbs free energy of 1.26 × 10 3 M −1 and −17.69 kJ mol −1 respectively were observed. [ABSTRACT FROM AUTHOR]

In this work, azide-funtionalised CdSe/ZnS QDs are conjugated with tetrakis(5-hexyn-oxy) Fe(II) phthalocyanine for the electrocatalytic detection of paraquat. The conjugate was fully characterised using various techniques to confirm the success of the reaction. They also showed good electrocatalytic ability towards the electroreduction of paraquat with limits of detection (LoD) of 5.9 × 10 −9 μM which is a great improvement compared to other reported sensors for this analyte. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards l -cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite. [ABSTRACT FROM AUTHOR]

A composite of multi-walled carbon nanotubes (MWCNT) with reduced graphene nanosheets (rGNS-2) was developed in order to minimize the restacking of the latter. The composite was used to modify a glassy carbon electrode (GCE). GCE was further modified with cobalt tetraamino phthalocyanine (CoTAPc). The modified electrode is represented as rGNS-2-MWCNT-CoTAPc-GCE. X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electrochemical microscopy and Raman spectroscopy were used to explore into surface functionalities, morphology and topography of the nanocomposite. The rGNS-2-MWCNT-CoTAPc-GCE had a low limit of detection of 3.32×10−8M towards the detection of paraguat as a test analyte. A mechanism for paraquat detection using an rGNS-2-MWCNT-CoTAPc-GCE is also proposed in this work. [ABSTRACT FROM AUTHOR]

We report on the electrodeposition of palladium nanoparticles (PdNPs) on a glassy carbon electrode (GCE) and onto a poly-CoTAPc-GCE (CoTAPc=cobalt tetraamino phthalocyanine) surface. The electrodes are denoted as PdNPs-GCE and PdNPs/poly-CoTAPc-GCE, respectively. PdNPs/poly-CoTAPc-GCE showed the best activity for the oxidation of hydrazine at the lowest potential of −0.28 V and with the highest currents. The results were further supported by electrochemical impedance spectroscopy (EIS) which showed that there was less resistance to charge transfer for PdNPs/poly-CoTAPc-GCE compared to PdNPs-GCE. The catalytic rate constant for hydrazine oxidation was 6.12×108 cm3 mol−1 s−1 using PdNPs/poly-CoTAPc-GCE. [ABSTRACT FROM AUTHOR]

Abstract: Cadmium tellurite quantum dots (CdTe-QDs) are linked to nickel tetraamino phthalocyanine (CdTe-QDs-NiTAPc) through an amide bond. Differential pulse voltammetry shows that that NiTAPc stabilizes the QDs against oxidative disintegration into metallic products on oxidation. Electrocatalytic oxidation of 2, 4-dichlorophenol (DCP) and pentachlorophenol (PCP) on CdTe-QDs and CdTe-QDs-NiTAPc adsorbed or electrodeposited onto a gold electrode were studied. Adsorbed CdTe-QDs-NiTAPc shows the lowest potential for DCP and PCP oxidation and it is also more stable to fouling by PCP and its oxidation products compared to adsorbed CdTe-QDs without NiTAPc. Electrodeposited CdTe-QDs or CdTe-QDs-NiTAPc show the best activity in terms of enhanced currents towards the oxidation of the chlorophenols. [Copyright &y& Elsevier]

Abstract: 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 3.70Amol−1 Lcm−2 for amitrole and diuron, respectively. The limits of detection were estimated to be 0.14 and 0.20μM for amitrole and diuron, respectively, using the 3δ notation. [Copyright &y& Elsevier]

Abstract: In this paper we report on synthesis and electrocatalytic behavior of cobalt (II)-tris(benzyl-mercapto)-monoaminophthalocyanine–single walled carbon nanotube nanorods towards the oxidation of amitrole. SWCNTs that were terminally functionalized with carboxylic acid groups were chemically linked to cobalt (II)-tris(benzyl-mercapto) monoaminophthalocyanine (CoMAPc) via an amide bond to form nanorods. UV–vis, FTIR, TEM, Raman and XRD spectroscopies were used in characterization of the nanorods (CoMAPc–SWCNT-linked), while cyclic voltammetry and chronoamperometry were used during the characterization of amitrole on the modified glassy carbon electrode. The linear dynamic range for the amitrole was from 1.0×10−6 M to 1.2×10−4 M, with a sensitivity of 6.76Amol−1 Lcm−2. The estimated limit of detection for amitrole was 0.10μM, using the 3δ criterion. The catalytic rate constant was found to be 1.09×105 M−1 s−1. [Copyright &y& Elsevier]

Abstract: In this paper, we report on the use of ethylene amine (EA) side-wall functionalized single-walled carbon nanotubes (SWCNT) in the synthesis of covalently linked cobalt (II) tetracarboxyl-phthalocyanine complex (CoTCPc–EA–SWCNT(linked)), the characterization of the linked complex and the application of this complex in the electrocatalytic oxidation of amitrole. UV–vis, FTIR, TEM, Raman and XRD spectroscopies were used in characterization of CoTCPc–EA–SWCNT complex, while cyclic voltammetry, rotating disc electrode (RDE) voltammetry, chronoamperometry and electrochemical impedance spectroscopy were used during the characterization of amitrole on the modified glassy carbon electrode. Thermogravimetric analysis (TGA) was used to confirm the extend of functionalisation of of SWCNTs. The catalytic rate constant was 1.2×103 M−1 s−1 and the apparent electron rate transfer constant was 3.0×10−5 cms−1. The linear dynamic range was 1.0×10−5–1.6×10−4 M, with a sensitivity of ∼0.76 A mol−1L cm−2 and a limit of detection of 0.1μM using the 3δ notation. [ABSTRACT FROM AUTHOR]

Abstract: In this work we report on the synthesis, characterization and the electrochemical behavior of amide linked nickel (II) tetraamino-phthalocyanine (NiTAPc)-single walled carbon nanotube (SWCNT) nanomaterials (NiTAPc-SWCNT (linked)). UV–vis, XRD, IR and Raman spectroscopies were used in characterization whilst cyclic voltammetry was used to study the electrochemical behavior of NiTAPc-SWCNT (linked)-GCE. Relative to the bare glassy carbon electrode (bare-GCE), SWCNT-GCE, NiTAPc-GCE, and NiTAPc/SWCNT (mixed)-GCE, the NiTAPc-SWCNT (linked)-GCE gave the best current responses for the oxidation of 2-mercaptoethanol (2-ME). The catalytic rate constant is of the magnitude of 103 M−1 s−1 while the detection limit (LOD) is 0.15μM using the 3δ notation, with a sensitivity of 2.53μAμM−1 cm−2. [Copyright &y& Elsevier]

Abstract: The facile electro-oxidation of diuron occurred at a glassy carbon electrode (GCE) modified with polymerized nickel tetraamino-phthalocyanine (NiTAPc), containing O–Ni–O bridges represented as poly-Ni(OH)TAPc-GCE. The oxidation of diuron occurred at a potential which is 60mV less than that of poly-NiTAPc (without O–Ni–O bridges) and was accompanied by enhanced catalytic currents. The catalytic rate constant and the diffusion constant were found to be 5.91×102 mol−1 Ls−1 and 6.43×10−6 cm2 s−1, respectively. The linear concentration range of diuron was 3.0×10−5 to 3.5×10−4 molL−1 with a limit of detection (LOD) of 3.3×10−7 molL−1 (3δ notation) and a sensitivity of 12.9Amol−1 Lcm−2. [Copyright &y& Elsevier]

Abstract: FeTAPc-single walled carbon nanotube (SWCNT) dendrimers are employed as glassy carbon electrode modifiers for the electrocatalytic oxidations of amitrole and diuron. The catalytic rate constants were 4.55×103 M−1 s−1 and 1.79×104 M−1 s−1 for amitrole and diuron, respectively using chronoamperometric studies. The diffusion constants were found to be 1.52×10−4 cm2 s−1 and 1.91×10−4 cm2 s−1 for diuron and amitrole, respectively. The linear concentration range for both were from 5.0×10−5 to 1.0×10−4 M and sensitivities of 0.6603μA/μM and 0.6641μA/μM for amitrole and diuron, with corresponding limits of detection of 2.15×10−7 and 2.6×10−7 M using the 3δ notation, respectively. [Copyright &y& Elsevier]

Abstract: In this paper we report on the synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single walled carbon nanotubes (CoTAPc–SWCNT-linked) for use as electrode surface modifiers. FTIR, UV–vis and Raman spectroscopies were used to ascertain the chemical linkage between CoTAPc and SWCNT while cyclic voltammetry and rotating disk electrode voltammetry were used to assess the electrocatalytic efficiency of the linked product towards the oxidation of 2-mercaptoethanol. The CoTAPc–SWCNT-linked-GCE demonstrated very good catalytic efficiency relative to CoTAPc–SWCNT-mixed-GCE, CoTAPc-GCE and f-SWCNTs-GCE (functionalised SWCNT). CoTAPc–SWCNT-linked-GCE gave a sensitivity of 0.2μA/μM and a limit of detection (LOD) of 1.2×10−7 M for 2-mercaptoethanol (2-ME) at pH 4. [Copyright &y& Elsevier]

Abstract: Cobalt and iron phenylthiosubstituted phthalocyanines have been deposited on Au electrode surfaces through the self-assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric and impedance techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of nitrite. The electrocatalytic parameters of the cobalt and iron phenylthiosubstituted phthalocyanines deposited on Au electrodes in nitrite solution were studied. Nitrite overpotentials which are lower than ever reported were obtained in this work for the iron phenylthiosubstituted phthalocyanines with very high stability. [Copyright &y& Elsevier]

Abstract: This work reports on the use of Co(II), Fe(II), Mn(III) and Ni(II) tetrakis benzylmercapto and dodecylmercapto phthalocyanine complexes for gold electrode modification for electrooxidation of sulphite ions. The complexes were successfully used to modify gold electrodes by self-assembled monolayer (SAM) technique. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, underpotential deposition (UPD) of copper and solution redox chemistry of [Fe(H2O)6 3+]/[Fe(H2O)6 2+]. All the modified electrodes showed improved catalytic activities than the unmodified gold electrode towards sulphite ion electrooxidation with all the modified electrodes exhibiting high resistance to electrode surface passivation. Better catalytic performance were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak, while the NiPcs which did not show metal based redox reaction performed less. The catalytic current was found to be linear with sulphite ion concentration in the concentration range employed in this work (0.1–1mM) and sensitivities ranging from 1.68 to 2.96μA/mM were observed for all the modified electrodes. Mechanisms of the catalytic oxidation of sulphite ions are proposed. [Copyright &y& Elsevier]

Abstract: This work reports on the use of nickel(II) tetrakis benzylmercapto (NiTBMPc) and dodecylmercapto (NiTDMPc) metallophthalocyanine complexes films on gold electrodes for the electrochemical oxidation of 4-chlorophenol (4-CP) and 2,4,5-trichlorophenol (TCP). Both NiTBMPc and NiTDMPc complexes were successfully deposited on gold electrodes by electropolymerisation. The films were electro-transformed in aqueous 0.1M NaOH solution to the ‘O–Ni–O oxo’ bridged form. For both complexes, films with different thickness were prepared and characterised by electrochemical impedance and UV–vis (on indium tin oxide) spectroscopies and the results showed typical behaviour for modified electrodes with increasing charge transfer resistance values (R p) with polymer thickness. The poly-Ni(OH)NiPcs showed better catalytic activity than their poly-NiPcs counterparts. [Copyright &y& Elsevier]

Abstract: This paper investigates the catalytic activities of arylthio substituted oxotitanium phthalocyanine (OTiPc) complexes that are immobilized on the glassy carbon electrode by electropolymerization, towards the oxidation of nitrite. The complexes are peripherally and non-peripherally substituted with phenylthio and benzylthio groups, namely 1a, 1b, 2a and 2b. All the modified electrodes exhibited improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a two-electron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ∼0.60V. Kinetic parameters are determined for all complexes and a mechanism is proposed. [Copyright &y& Elsevier]

Abstract: This work reports on the electrooxidation of nitrite using Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines electrodeposited onto a gold electrode. Good catalytic activity (in terms of lowering overpotential) was obtained for these molecules when compared to previously reported MPc catalysts. The catalytic current was found to vary linearly with nitrite concentration in the range employed in this work (0.1–1mM) and high sensitivities ranging from 6.9 to 9.9μAmM−1 were observed for all the modified electrodes. [Copyright &y& Elsevier]

Abstract: Catalytic activity of cobalt tetra ethoxythiophene and cobalt tetra phenoxypyrrole phthalocyanine complexes towards oxidation of 2-mercaptoethanol, l-cysteine and reduced glutathione is reported. It was found that the activity of the complexes depends on the substitution of the phthalocyanine ring, pH, film thickness and method of electrode modification. The high electrocatalytic activity obtained with adsorbed complexes in alkaline medium clearly demonstrates the necessity of modifying bare carbon electrodes to endow them with the desired behaviour. [Copyright &y& Elsevier]

Abstract: Comparative surface electrochemistry and electrocatalytic properties of solid ultrathin monolayer films of metallophthalocyanine (MPc) complexes of cobalt (CoPc), iron (FePc) and manganese (MnPc) self-immobilised, via axial ligation reaction, onto preformed 4-mercaptopyridine self-assembled monolayers (SAMs) on gold electrodes have been described. Surface electrochemical parameters of the modified electrodes showed that these MPc-SAMs are densely packed with flat orientations. The electrochemical, electrocatalytic and stability properties of these MPc complexes follow this order: FePc>MnPc>CoPc. This finding is remarkable as it suggests that the success of using this method of self-assembling of MPc onto gold electrode is largely dependent on the bond distance between the pyridine linker and the central metal of the MPc; the shorter the distance, the faster the co-ordination and the better the electrocatalytic properties towards l-cysteine and thiocyanate. Thus, the superiority of FePc-based SAM over those of the MnPc and CoPc, has been proposed to be the result of the more favorable axial co-ordination properties of FePc with pyridine (i.e. shorter Fe–N(pyridine) bond length. [Copyright &y& Elsevier]

Abstract: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using l-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine l-cysteine at concentrations between 0.0015 and 1mM in pH 4 aqueous conditions. [Copyright &y& Elsevier]

Abstract: Electrocatalytic oxidation and detection of hydrazine in pH 7.0 conditions were studied by using gold electrode modified with self-assembled monolayer (SAM) films of iron phthalocyanine (FePc) complex axially ligated to a preformed 4-mercaptopyridine SAMs. The anodic oxidation of hydrazine in neutral pH conditions with FePc-linked-mercaptopyridine-SAM-modified gold electrode occurred at low overpotential (0.35V versus Ag|AgCl) and the treatment of the voltammetric data showed that it was a pure diffusion-controlled reaction with the involvement of one electron in the rate-determining step. The mechanism for the interaction of hydrazine with the FePc-SAM is proposed to involve the Fe(III)Pc/Fe(II)Pc redox process. Using cyclic voltammetry (CV) and Osteryoung square wave voltammetry (OSWV), hydrazine was detected over a linear concentration range of 1.3×10−5 to 9.2×10−5 mol/L with low limits of detection (ca. 5 and 11μM for OSWV and CV, respectively). At concentrations higher than 1.2×10−4 mol/L the anodic peak potential shifted to 0.40V (versus Ag|AgCl), and this was interpreted to be due to kinetic limitations resulting from the saturation of hydrazine and its oxidation products onto the redox-active monolayer film. This type of metallophthalocyanine-SAM-based electrode is a highly promising electrochemical sensor given its ease of fabrication, good catalytic activity, stability, sensitivity and simplicity. [Copyright &y& Elsevier]

Abstract: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 moldm−3) with a detection limit in the order of ∼10−7 moldm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity. [Copyright &y& Elsevier]

Abstract: A new family of thiol-derivatized metallophthalocyanine has been synthesized. The electrochemical behaviors of the complexes have been investigated. The modified glassy carbon electrode using the electropolymerized manganese complex (poly-MnTMPyrPc) was characterized in aqueous solution. The result indicates that the complexes are easier to electropolymerize in dichloromethane (DCM) than in dimethylformamide (DMF). The poly-MnTPyrPc-modified electrode showed pH dependence within the pH range studied (2–8). The cathodic wave of the electrode showed more pH dependence than the anodic wave. Poly-MnTPyrPc could catalyse the reduction of oxygen. [Copyright &y& Elsevier]

Chromium tetraaminophthalocyanine (CrIIITAPc) has been synthesized and its electrochemical and spectroelectrochemical properties reported. The first reduction and oxidation in this complex occur at the central metal, giving CrIITAPc and CrIVTAPc complexes, respectively, the latter having been observed for the first time. The CrIIITAPc species was polymerized onto glassy carbon (GCE) or indium tin oxide (ITO) electrodes and the polymer evolution confirmed by UV/Visible spectroscopy and by scanning electron microscopy. The polymers were employed for the catalytic oxidation of nitrite or nitric oxide, and the catalysis involved the CrIVTAPc−1 species. [Copyright &y& Elsevier]

Manganese tetraaminophthalocyanine (MnTAPc) has been synthesised. The cyclic voltammetry and spectroelectrochemistry of the complex have been examined. Spectroelectrochemistry has been used to confirm that the species synthesised in this work contains MnIII, giving (OH)MnIIITAPc. The oxidation and reduction couples obtained from cyclic voltammetry have been assigned to MnIVPc−/MnIVPc2− (couple I), MnIVPc2−/MnIIIPc2− (couple I′), MnIIIPc2−/MnIIPc2− (couple II) and MnIIPc2−/MnIIPc3− (couple III). Electropolymerization of the MnTAPc onto either the indium tin oxide or glassy carbon electrode results in the in the formation of a poly-MnTAPc. The poly-MnTAPc shows improved reversibility at low pH. The poly-MnTAPc electrode was employed to analyse glycine. [Copyright &y& Elsevier]