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.     

Electrode modification using nanocomposites of electropolymerised cobalt phthalocyanines supported on multiwalled carbon nanotubes

Journal of Solid State Electrochemistry - A polymer of tetra(4)-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) has been deposited over a multiwalled carbon nanotube (MWCNT)...     

Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes

Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (k_app) for the electrodes is 2.2?×?10^?5 cm.s^?1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The k_app values for the bare and benzylamino modified electrodes were found to be 1.2?×?10^?4 cm.s^?1 and 4.9?×?10^?6 cm.s^?1, respectively. The electrocatalysis of the modified electrodes towards detection of H₂O₂ gave significant peak current densities and electrocatalytic potentials at ?0.28 V and ?0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.     

Reaction of Perrhenate with Phthalocyanine Derivatives in the Presence of Reducing Agents and Rhenium Oxide Nanoparticles in Biomedical Applications

A novel alternative route to access rhenium(V)−phthalocyanine complexes through direct metalation of metal-free phthalocyanines (H₂Pcs) with a rhenium(VII) salt in the presence of various two-electron reducing agents is presented. Direct ion metalation of tetraamino- or tetranitrophthalocyanine with perrhenate (ReO₄⁻) in the presence of triphenylphosphine led to oxidative decomposition of the H₂Pcs, giving their respective phthalonitriles. Conversely, treatment of H₂Pcs with ReO₄⁻ employing sodium metabisulfite yielded the desired Re^VO−Pc complex. Finally, reaction of H₂Pcs with ReO₄⁻ and NaBH₄ as reducing agent led to the formation of rhenium oxide (Re_xO_y) nanoparticles (NPs). The NP synthesis was optimised, and the Re_xO_y NPs were capped with folic acid (FA) conjugated with tetraaminophthalocyanine (TAPc) to enhance their cancer cell targeting ability. The cytotoxicity profile of the resultant Re_xO_y−TAPc−FA NPs was assessed and found to be greater than 80 % viability in four cell lines, namely, MDA−MB-231, HCC7, HCC1806 and HEK293T. Non-cytotoxic concentrations were determined and employed in cancer cell localization studies. The particle size effect on localization of NPs was also investigated using confocal fluorescence and transmission electron microscopy. The smaller NPs (≈10 nm) were found to exhibit stronger fluorescence properties than the ≈50 nm NPs and exhibited better cell localization ability than the ≈50 nm NPs.     

Iodine‐Doped Cobalt Phthalocyanine Supported on Multiwalled Carbon Nanotubes for Electrocatalysis of Oxygen Reduction Reaction

4‐(4,6‐Diaminopyrimidin‐2‐ylthio) phthalocyaninatocobalt(II) (CoPyPc) was iodine doped, and its electrocatalytic properties explored. Physical characterization techniques such as UV‐vis, X‐ray photoelectron, electron paramagnetic resonance and infra‐red spectroscopy were used. Cyclic voltammetry, electrochemical impedance spectroscopy and rotating disk electrode were used for electrochemical characterization of electrodes modified with the prepared phthalocyanine and its nanocomposites. The electrocatalytic effect of a new iodine‐doped cobalt phthalocyanine derivative supported on multiwalled carbon nanotubes was then investigated towards oxygen reduction reaction. The electrocatalytic activity of the iodine‐doped cobalt phthalocyanine was found to be superior in terms of current over the undoped phthalocyanine nanocomposite.     

The effects of carbon nanotubes on the electrocatalysis of hydrogen peroxide by metallo-phthalocyanines

The pre-grafted screen-printed gold electrode modified with phenyl-amino monolayer was investigated for covalent immobilization of phenyl-amine functionalized single-walled carbon nanotubes (PA-SWCNT) and metal tetra-amino phthalocyanine (MTAPc) using Schiff-base reactions with benzene-1,4-dicarbaldehyde (BDCA) as cross-linker. The PA-SWCNT and MTAPc modified electrodes were applied as hybrids for electrochemical sensing of H₂O₂. The step-by-step fabrication of the electrode was followed using electrochemistry, impedance spectroscopy, scanning electron microscopy and Raman spectroscopy and all these techniques confirmed the fabrication and the immobilization of PA-SWCNT, MnTAPc and CoTAPc onto gold surfaces. The apparent electron transfer constant (k_app) showed that the carbon nanotubes and metallo-phthalocyanines hybrids possess good electron transfer properties compared to the bare, pre-grafted and the MTAPc modified gold electrode surfaces without PA-SWCNT. The electrochemical sensing of hydrogen peroxide was successful with PA-SWCNT-MTAPc hybrid systems showing higher electrocatalytic currents compared to the other electrodes. The analytical parameters obtained using chronoamperometry gave good linearity at H₂O₂ concentrations ranging from 1.0 to 30.0 μmol L⁻¹. The values for the limit of detection (LoD) were found to be of the orders of 10⁻⁷ M using the 3δ for all the electrodes. The PA-SWCNT-MTAPc modified SPAuEs were much more sensitive compared to PA-MTAPc modified SPAuEs.     

Nanomagnet Bioconjugates with anti-CRP Polyclonal Antibodies as Nanobioprobes for Enhanced Impedimetric Detection of CRP

Selective purification of biological materials for their detection in complex sample matrix is a general challenge for many researchers working in the field of diagnostics. Magnetic nanoparticles functionalized with biological molecules that impart biomolecular selectivity are therefore of major interest as capture probes thus allowing for magnetic separations. Nanoparticles can also be used for the enhanced detection of biomarkers. In this work, an ultrasensitive sandwich-based impedimetric immunosensor was fabricated for the detection of C-reactive protein antigen (CRPAg). Stable and oriented immobilization of anti-CRP monoclonal antibody was achieved onto electrografted phenylethylamine derivatized with succinic anhydride and phenylboronic acid via carbodiimide chemistry. The detection of CRPAg was achieved using Electrochemical Impedance Spectroscopy (EIS). The enhancement of the impedance charge-transfer resistance (R_CT) signal was achieved using the sandwich approach. The anti-CRP polyclonal antibody was immobilized in an oriented manner onto magnetic nanoparticles functionalized with phenylboronic acid. The increase in the change in charge-transfer resistance (ΔR_CT) values was linearly proportional to the concentration of CRPAg in the range 10 to 200 ng mL⁻¹ covering the clinical range for CRPAg detection and with a detection limit of 0.34 ng mL⁻¹.