The electrocatalytic activity of metallophthalocyanines and their conjugates with carbon nanomaterials and metal tungstate nanoparticles
- Authors: Ndebele, Nobuhle
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Nitrites , Dopamine , Catechol , Detection limit
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/431934 , vital:72816 , DOI 10.21504/10962/431933
- Description: In this dissertation, seventeen phthalocyanine complexes were synthesised. Of these, only four are known and have been published. These complexes were synthesised using the conventional statistical condensation method that involves refluxing the phthalonitrile(s) (4-((1,3-bis(dimethylamino)propan-2-yl)oxy)phthalonitrile, 4-(4-carboxyphenoxy)phthalonitrile, 4-(4-acetylphenoxy)phthalonitrile, dimethyl 5-(3,4-dicyanophenoxy)-isophthalate, 4-(4-(tert-butyl)phenoxy)phthalonitrile, 5-phenoxylpicolinic acid phthalonitrile 4-(4-formylphenoxy) phthalonitrile, and 4-(4-(3-oxo-3-phenylprop-1-enyl) phenoxy) phthalonitrile) with the metal salt and 1,8-diazabicyclo[5.4.0]undecane as a catalyst in a high-temperature solvent. And thereafter (when necessary), isolation and purification of the target compounds were achieved through the use of silica column chromatography. These compounds were characterised using various analytical techniques such as; ultraviolet-visible absorption, mass spectroscopy, and Fourier transform infrared spectra and elemental analysis. These techniques proved that the complexes were successfully synthesised and isolated as pure compounds. Carbon-based (graphene quantum dots and nitrogen-doped graphene quantum dots) and metal oxide (bismuth tungsten oxide and nickel tungsten oxide) nanomaterials were synthesised. Together with the purchased single-walled carbon nanotubes, these nanomaterials were conjugated to some of the MPc complexes via non-covalent (carbon-based nanomaterials) and covalent (metal oxides) linkage forming hybrid materials. These nanomaterials and hybrids were characterised using various analytical methods (ultraviolet-visible absorption, X-ray diffraction, Raman spectroscopy, thermographic analysis, and dynamic light scattering). Nanomaterials were utilised herein to determine their effect on the properties of MPc complexes and provide a synergistic effect in the hope of enhancing these properties. All complexes synthesised in this work (MPcs, nanomaterials and hybrids) were employed as electrocatalysts in electrochemical sensing. These electrocatalysts were embedded onto the glassy carbon electrode via an adsorption method known as drop-casting. The modified electrode surfaces were characterised using cyclic voltammetry, electrochemical impedance spectroscopy and scanning electrochemical microscopy to determine various electrochemical parameters. These electrocatalysts were used in the detection of either nitrite, catechol and/or dopamine. The detection limits, sensitivities, kinetics and catalytic constants were among other parameters determined for each electrocatalyst. These electrocatalysts proved to be stable electrocatalysts that could potentially be used for practical applications. The determined parameters were comparable and sometimes better than those obtained in literature. , Thesis (PhD) -- Faculty of Science, Chemistry, 2023
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- Date Issued: 2023-10-13
Low-Symmetry Phthalocyanines Bearing Carboxy-Groups
- Authors: Bunin, Dmitry A , Ndebele, Nobuhle , Martynov, Alexander G , Mack, John , Gorbunova, Yulia G , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231262 , vital:49870 , xlink:href="https://doi.org/10.3390/molecules27020524" "
- Description: The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.
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- Date Issued: 2022
The Electrocatalytic Detection of Nitrite Using Manganese Schiff Base Phthalocyanine Complexes
- Authors: Ndebele, Nobuhle , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295856 , vital:57385 , xlink:href="https://doi.org/10.1007/s12678-022-00752-4"
- Description: This work investigates the use of manganese phthalocyanines (MnPcs) in the electrochemical detection of nitrite. These are two Schiff base derivatives: tetrakis 4-(4-thio-thiophene-2-ylmethanamino) phthalocyaninato Mn(III)Cl (2) and tetrakis 4-(3-(pyrrolidine-1-yl)propan-1-amino)phthalocyaninato Mn(III)Cl (3) and one aldehyde: tetrakis(4-formylphenoxy)phthalocyaninato Mn(III)Cl (1). The MnPc complexes were adsorbed onto the glassy carbon electrode surface using the drop-dry method and used as electrocatalysts to detect nitrite. Nitrite oxidation peak potentials obtained using cyclic voltammetry ranged between 0.70 and 0.84 V. Detection limits as low as 0.16 µM and sensitivity values as high as 276 µMmM−1 were obtained through the use of chronoamperometry. The Schiff base MnPcs 2 and 3 exhibited better nitrite detection properties (in terms of limit of detection and sensitivity) than their aldehyde precursor (1).
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- Date Issued: 2022
Electrocatalytic Activity of Cobalt Phthalocyanines Revisited: Effect of the Number of Oxygen Atoms and Conjugation to Carbon Nanomaterials
- Authors: Ndebele, Nobuhle , Mgidlana, Sithi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185700 , vital:44416 , xlink:href="https://doi.org/10.1007/s12678-021-00670-x"
- Description: The synthesis and characterization of tetrakis[4(4-acetlyphenoxy)phthalocyanato] cobalt (II) (1) are presented. Complex 1 together with the reported tetrakis dimethyl 5-(phenoxy)-isophthalatephthalocyaninato] cobalt (II) (2) are conjugated to carbon-based nanomaterials: graphene quantum dots (GQDs) and single-walled carbon nanotubes (SWCNTs) via π-π stacking, taking advantage of the π electrons on the graphitic structure of the nanomaterial as well as on the aromatic rings of the Co phthalocyanines (CoPcs). The electrocatalytic behaviour of the CoPcs, GQDs, SWCNTs and their respective conjugates towards the electrochemical oxidation of catechol was studied. The electrocatalytic probes were drop-dried onto the electrode surface of the glassy carbon electrode (GCE). The electrochemical oxidation of catechol was studied using cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry. Complex 2 when linked to GQDs gave the lowest oxidation peak potentials of 0.33 V. Low catechol detection limits (LOD) of 0.057 µM was obtained for complex 2 with SWCNT. Thus, complex 2 containing more oxygen atoms outperformed complex 1 with less oxygen atoms. The CoPcs on their own showed moderate electrocatalytic behaviour, hence showing the importance of conjugating them to the carbon nanomaterials. SWCNT-based electrodes performed better than GQDs, and an improvement in the LoDs, sensitivity and the catalytic rate was observed upon conjugation.
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- Date Issued: 2021
Electrocatalytic activity of Schiff base containing copper phthalocyanines towards the detection of catechol
- Authors: Ndebele, Nobuhle , Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231410 , vital:49885 , xlink:href="https://doi.org/10.1016/j.poly.2021.115518"
- Description: In this study, four new copper phthalocyanine complexes were synthesised and studied as electrocatalysts for the detection of catechol. Two of these complexes were derived from a symmetrical benzaldehyde phthalocyanine complex via the condensation of the benzaldehyde substituents with amine reagents. The electrocatalysts proved to be highly stable towards the detection of catechol. The oxidation peaks obtained using cyclic voltammetry range from 0.20 to 0.38 V. Detection limits were obtained via chronoamperometry and are as low as 0.16 µM with fairly high sensitives being obtained. Overall all four copper complexes exhibited excellent electrocatalytic activity towards the electrooxidation of catechol.
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- Date Issued: 2021
A 3, 5-DistyrylBODIPY Dye Functionalized with Boronic Acid Groups for Direct Electrochemical Glucose Sensing
- Authors: Ndebele, Nobuhle , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187556 , vital:44671 , xlink:href="https://doi.org/10.1002/elan.201800651"
- Description: The synthesis and characterization of a novel BODIPY dye functionalized with bis-boronic acid groups to enable direct glucose sensing through selective recognition of carbohydrates is reported. Styrylation with boronic acid groups at the 3,5-positions of the BODIPY core results in an extension of the π-conjugation system of the dye and in a red-shift of the main absorption band from 500 to 637 nm. The functionalized BODIPY dye was adsorbed on a glassy carbon electrode using the drop and dry method. Modified and bare electrodes were characterized using cyclic voltammetry and scanning electrochemical microscopy, while glucose detection was carried out by using differential pulse voltammetry and chronoamperometry. The detection limit was determined to be 1.42 μM. The dye was found to be selective and sensitive towards glucose, since likely interferences have only minor effects on the glucose detection.
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- Date Issued: 2019
BODIPY and porphyrin dyes for direct glucose sensing and optical limiting applications
- Authors: Ndebele, Nobuhle
- Date: 2019
- Subjects: Boron compounds , Boric acid , Porphyrins , Dyes and dying -- Chemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/97221 , vital:31412
- Description: A series of BODIPY dyes functionalised with boronic acid in the 3,5-positions were successfully synthesised and characterised by using various analytical techniques. The dyes were prepared through a slight modification of the conventional acid catalysed condensation method. Phenylboronic acid moieties were added as styryl groups at the 3,5-positions of the 1,3,5,7-tetrametylBODIPY cores using a modified Knoevengal condensation method. The addition of the styryls resulted in the main absorption band of the dyes red-shifting to the 630−650 nm region. The photophysical and electrochemical properties of these dyes were studied to determine whether the dyes are suitable for use in the fluorescent, colourimetric and electrochemical detection of glucose. Boronic acid moieties were added as bioreceptor recognition elements because they have an affinity for carbohydrates and therefore would be able to bind and “detect” glucose. The series of BODIPY dyes did not show a “turn-on” fluorescence effect upon addition with glucose at the physiological pH. This was attributed on the basis of molecular modelling to the absence of an MO localised on the boronic-acid-substituted styryl moieties that lie close in energy to the HOMO and LUMO that facilitates the formation of an intramolecular charge transfer state. However, colourimetric changes that are visible to the naked eye are observed at basic pH when glucose was added to the dye solutions. The dyes exhibited favourable electrochemical behaviour and were able to detect glucose directly in this context when glassy carbon electrodes are modified through the drop dry method. A series of Sn(IV) porphyrins with thienyl and phenyl groups at the meso-positions were successfully synthesised and characterised. Pyridine and tetrabutyl axial ligands were added to the porphyrins to limit aggregation. The optical limiting properties of these porphyrins and three styrylated BODIPY dyes were studied in benzene and dichloromethane. Dyes were also embedded in polystyrene and studied as thin films to further gauge their suitability for use in optical limiting applications. Second-order hyperpolarizability, third-order susceptibly, non-linear absorption with reversible saturable absorption and the optical limiting threshold, were the parameters studied. Three of the four porphyrins and the three styrylated BODIPY dyes showed favourable optical limiting behaviour, which was further enhanced when the dyes are embedded in polymer thin films.
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- Date Issued: 2019
Porphyrin dimers with a bridging chiral amide-bonded benzo-moiety
- Authors: Liang, Xu , Qin, Mingfeng , Zhou, Lin , Liu, Tingting , Li, Minzhi , Mack, John , Ndebele, Nobuhle , Nyokong, Tebello , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233433 , vital:50090 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.02.043"
- Description: The facile synthesis and characterization of four porphyrin dimers which introduced stereomeric centers with chiral amide-bonded para- and meta-disubstituted benzo-moiety is reported. Trends in the electronic structures and optical and redox properties are analyzed through a comparison with theoretical calculations to explore the effect of positional isomerism of the bridging benzene rings.
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- Date Issued: 2018