List of Titles

Carbonylation of cyclohexene with carbon dioxide (CO2) using transition metals as heterogeneous and homogeneous catalysts

- Sekaleli, Bafokeng Thabelo

Authors: Sekaleli, Bafokeng Thabelo
Date: 2024-10-11
Subjects: Uncatalogued
Language: English
Type: Academic theses , Master's theses , text
Identifier: http://hdl.handle.net/10962/464565 , vital:76522
Description: From a green chemistry perspective, carbon dioxide (CO2) emerges as an appealing C1 synthon, given its abundance in the atmosphere and cost-effectiveness. Many essential chemicals for daily life are derived from fossilized carbon sources like coal, petroleum, and natural gas. However, the by-product of these processes, CO2, poses environmental risks when excessively emitted as a greenhouse gas. Achieving a balance between carbon emissions and removal is crucial to address environmental concerns surrounding CO2. Utilizing CO2 as a C1 source in organic synthesis holds promise for mitigating this balance in the long term. Combining CO2 with other underutilized fine chemicals, such as alkanes, alkenes, and alkynes, to produce more valuable platform chemicals presents an economically viable strategy due to carbon dioxide’s abundance, low cost, and recyclability. Despite its simplicity, CO2's high thermodynamic stability and low kinetic reactivity, owing to its highly oxidized state, pose challenges to its use as a feedstock. Overcoming these hurdles requires catalysts to enhance CO2 reactivity. Our work focuses on developing and employing catalytic systems capable of activating CO2 as a C1 synthon in reactions with cyclohexene and a reducing agent to yield carboxylic acids or esters. In one approach, we have developed heterogeneous catalyst systems comprising transition metals (Au, Fe, Ni, Ru) supported on metal oxide (TiO2). Characterization techniques such as TEM, EDX, UV-Vis, BET, and XRD were used to study the properties of these materials. The catalysts were evaluated in a reaction involving cyclohexene, CO2, and H2O. In another approach, we explored the use of cyclo-tris(tetracarbonylruthenium) [Ru3(CO)12] as a homogeneous catalyst in a reaction involving cyclohexene, methanol, and CO2 in the presence of an ionic liquid, 1-Butyl-3-methylimidazolium chloride ([BMIM]+Cl-). 1H NMR and ATR-FT-IR were utilized to characterize [BMIM]+Cl-. The reaction product was characterised utilizing GC-MS. Upon seeing that Ru3(CO)12 changes color from orange to black when exposed to heat, an investigation was undertaken on the kind of transformations that the catalyst undergoes. This investigation was carried out with the hopes of finding the structures that could be resulting from Ru3(CO)12 during the reaction and their significance to it. The orange and black Ru complexes were characterized utilizing DSC, TGA, ATR-FT-IR and PXRD. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-10-11

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Co-crystal formation of pharmaceutical and veterinary tranquilizer molecules

- Mngwengwe, Bongeka Naledi Precious

Authors: Mngwengwe, Bongeka Naledi Precious
Date: 2024-10-11
Subjects: Uncatalogued
Language: English
Type: Academic theses , Master's theses , text
Identifier: http://hdl.handle.net/10962/464532 , vital:76519
Description: Midazolam, a 1,4-benzodiazepine derivative is commonly used to treat anxiety, insomnia and may be used as a sedative in anaesthesia as it has calming, anti-convulsant and muscle relaxant properties. Midazolam has a rapid onset but a short duration of action resulting in fewer adverse effects. Midazolam also has the potential to form insoluble crystalline precipitates in pharmaceutical dosage forms such as syrups and solutions, which is a challenge in formulation and process development activities. The primary goal of this research was to prepare multicomponent crystals of midazolam free base, specifically targeting interactions with coformers structurally similar to methyl paraben. Key preparation techniques included neat grinding, liquid-assisted grinding, and slow evaporation. The resulting solid forms were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), and powder X-Ray Diffraction (PXRD). In addition, Single-Crystal X-Ray Diffraction (SCXRD) was used to elucidate detailed structural information on the novel multicomponent crystals formed. Successful preparation of midazolam free base from the hydrochloride salt was confirmed through FTIR, DSC, and PXRD analysis. Different co-crystals and salts of midazolam with coformers such as salicylic acid (SA), benzoic acid (BA), 3-hydroxybenzoic acid (3-HBA) and p-aminobenzoic acid (PABA) were synthesized and characterized. The structure of the single crystal obtained from a veterinary tranquilizer solution was solved and found to be a salt that had formed between midazolam free base, midazolam HCl, and methyl paraben. This finding inspired further investigation of similar multicomponent crystals of midazolam and methyl paraben analogues. This study demonstrated the effectiveness of both mechanochemical and slow evaporation methods for the preparation of multicomponent crystals. PXRD and DSC provided insights into the stability and purity of the crystals that had formed and the differences in melting points and PXRD patterns were particularly important in this regard. Differences in FTIR spectra were used to distinguish between different solid forms and to confirm the successful formation of new solid forms. Extensive searches in the Cambridge Structural Database (CSD) confirmed that the multicomponent crystals of midazolam, such as MDZ‧SA, MDZ‧BA, MDZ‧3-HBA, and MDZ‧PABA, had not previously been reported, highlighting the novelty of these findings. The research successfully isolated and characterized several novel multicomponent crystals of midazolam, demonstrating the potential of mechanochemistry and solvent evaporation techniques in the development of pharmaceutical and veterinary medicinal applications. These findings contribute to the understanding of cocrystal formation and provide a foundation for future studies in which the stability and efficacy of midazolam-based formulations can be evaluated. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-10-11

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Cocrystals, salts and eutectics of anti-tuberculosis medicines

- Matlapeng, Tsebang Alice

Authors: Matlapeng, Tsebang Alice
Date: 2024-10-11
Subjects: Uncatalogued
Language: English
Type: Academic theses , Master's theses , text
Identifier: http://hdl.handle.net/10962/464521 , vital:76518
Description: Tuberculosis remains as a prominent cause of death worldwide. This infectious disease is treated with first and second line drugs. However, challenges of multi drug resistant tuberculosis and adverse side effects such as depletion of essential B group vitamins in the body by first line drugs, as well as poor physicochemical properties of second line drugs persist. Cocrystallisation of anti-tubercular drugs with various coformers has therefore been used as an alternative method to improve the physicochemical properties of active pharmaceutical ingredients (API) while maintaining their efficacy. The main objective of this study was to carry out cocrystal screening of anti-tubercular API and vitamin B coformers to make drug-drug or drug-vitamin multicomponent complexes. Preparation of the multicomponent complexes was carried out by mechanochemical grinding (neat grinding (NG), liquid assisted grinding (LAG) and slow evaporation. All complexes were characterised using Fourier-transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and crystal structures were elucidated using single-crystal X-ray diffraction (SCXRD). The cocrystal screening resulted in the formation of various solid forms, which included cocrystals, salts and eutectic products. Two cocrystals of 4-aminosalicylic acid (PAS) were isolated and characterised. The cocrystal of PAS with isoniazid (INH) demonstrated similar characteristics for both the bulk crystalline material and milled materials. The cocrystal of PAS and pyrazinamide (PYR) prepared using mechanochemical synthesis was met with challenges, while difficulties were also encountered in obtaining suitable crystals for SCXRD analysis. The ground and recrystallised samples of the PAS and pyrazinecarboxylic acid (PCBA) showed distinct differences in their thermal behaviour, with SCXRD revealing the decomposition product phenolammonium-pyrazinecarboxylate salt ‘sans’ the CO2 moiety. Salt formation involving pyridoxine (PN) yielded a salt hydrate with PAS (PN-PAS) and an anhydrous salt with PCBA (PN-PCBA). Both salts exhibited very complex packing arrangements with equally complex thermal behaviour depending on the solvent used during preparation, and the method of preparation. Three eutectic systems involving INH with PYR, PN and pyridoxine hydrochloride (PNꞏHCl) were identified, and their phase diagrams were constructed from DSC data. The eutectic compositions obtained were 1:1 for INH:PYR, 1:1 for INH:PN and 6:4 for INH:PNꞏHCl. Finally, a total of eight multicomponent complexes were prepared using selected API and vitamin B6 components. The results presented here provide motivation for further investigation and evaluation of the pharmacochemical properties of these API. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-10-11

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Metallophthalocyanines: versatile probes for microbial photoinactivation and for pollutant degradation as photocatalysts, both molecular or supported form

- Sindelo, Azole

Authors: Sindelo, Azole
Date: 2024-10-11
Subjects: Uncatalogued
Language: English
Type: Academic theses , Doctoral theses , text
Identifier: http://hdl.handle.net/10962/466614 , vital:76760 , DOI https://doi.org/10.21504/10962/466614
Description: This thesis investigates the synthesie of metallophthalocyanines for potential use as photosensitizers in two applications: photodynamic antimicrobial chemotherapy and the photodegradation of organic pollutants. To achieve this, phthalocyanines with morpholine (substituted at alpha and beta position, to imine), ethyl and propyl pyrrolidine Schiff bases, asymmetrical mercaptobenzothiazole and morpholine substituents were synthesized for the first time. All nitrogen containing phthalocyanines were methylated to form cationic derivatives. Asymmetrical mercaptobenzothiazole were covalently linked to spherical and pyramidal zinc oxide nanoparticles, while the asymmetrical morpholine were conjugated to polyacrylonitrile (PAN) nanofibers, chitosan modified PAN and glass wool, while carboxylic acid containing phthalocyanines were also linked to glass wool. Various characterization techniques, including electronic spectroscopy, mass spectroscopy, nuclear magnetic resonance (NMR), Fourier-transform infrared (FT-IR), elemental analysis, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscope (SEM), and time-resolved fluorescence measurements were employed to characterize all the phthalocyanine composites. The research aimed to establish general trends in fluorescence quantum yields, triplet and singlet oxygen generation, photodegradation rates, and fluorescence and triplet state lifetimes of the complexes. Notably, the presence of zinc oxide nanoparticles increased the triplet quantum yield of phthalocyanines, however, the singlet oxygen quantum yield decreased. The study also examined the photodynamic inactivation of various planktonic cells and biofilms using all photosensitizers. The photodynamic antimicrobial chemotherapy activities were dose-dependent, and all cationic photosensitizers were highly effective in completely inactivating the microbes in both forms, as opposed to non-charged photosensitizers. For the supports, the chitosan modified PAN showed high efficacy due to improved hydrophilicity. Furthermore, the research was conducted on the photodegradation of 4-chlorophenol, methyl orange and methylene blue using Pc-anchored PAN and glass wool supports. The immobilized photosensitizers demonstrated a strong capacity for generating singlet oxygen in aqueous media, with the cationic Pc-PAN removing methylene blue more efficiently due to its adsorption and photodegradation abilities. All supports were recoverable, showing potential application for future use in the removal of microbes and organic pollutants. , Thesis (PhD) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-10-11

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Photodynamic anticancer and antimicrobial activities of aza-BODIPY and porphyrinbased photosensitisers and their non-linear properties

- Molupe, Nthabeleng Regina

Authors: Molupe, Nthabeleng Regina
Date: 2024-10-11
Subjects: Uncatalogued
Language: English
Type: Academic theses , Doctoral theses , text
Identifier: http://hdl.handle.net/10962/466603 , vital:76758 , DOI https://doi.org/10.21504/10962/466603
Description: New aza-BODIPY dyes and porphyrins were synthesised and characterised so that photodynamic therapy (PDT) and photodynamic antimicrobial chemotherapy (PACT) activity studies could be performed. Several strategies were explored to achieve targeted nanoplatforms or biocompatible nanoplatforms to enhance the suitability of these compounds for use in PDT. Following earlier MSc research on the encapsulation of halogenated boron dipyrromethene (BODIPY) dyes into Pluronic® micelles, similar nanomicelles were prepared to encapsulate halogenated boron aza-dipyrromethene (aza-BODPY) dyes to enhance their aqueous solubility. However, the 1,7-dimethylthiophenyl- 2,6-diiodo-3,5-diphenyl (1) and 1,7-di-methylthiophenyl-2,6-diiodo- 3,5-dithien-3-yl (2) aza-BODIPY dyes that were prepared in this context were found to degrade when encapsulated. A different strategy was then followed in which gold nanoparticles (AuNPs) were conjugated to 1 and 2 via Au-S interactions to form biocompatible aza-BODIPY-AuNP conjugates (1-AuNP and 2-AuNP). This strategy was successful, and favourable IC50 values of 3.60 and 10.0 μM for 1-AuNP and 2- AuNP were obtained during in vitro PDT activity studies against MCF-7 human breast cancer cells, respectively, while values of 11.0 and 12.8 μM were obtained for 1 and 2. To further explore the preparation of better-targeted aza-BODIPY photosensitiser dyes, folic acid (FA) was conjugated to 1,7-dihydroxyphenyl-2,6-diiodo-3,5-di-4- bromophenyl (3) and 1,7-di-4-bromo-2,6-diiodo-3,5-dihydroxyphenylphenyl (4) aza- BODIPYs via ester bonds. Not only was the conjugation to form 3-FA and 4-FA successful, but the conjugated dyes are water-soluble, which is advantageous for drug transport in the context of PDT. These conjugates were applied in vitro against MCF-7 cancer cells and were found to have relatively high activities with IC50 values of 0.91 and 7.48 μM for 3-FA and 4-FA, respectively, while values of 11.3 and 13.0 μM were obtained for the non-conjugated 3 and 4 dyes. In a similar manner, tin (IV) and indium (III) tetrapyridylporphyrins (5 and 6) were axially conjugated to folic acid via ester bonds (5-FA and 6-FA). The conjugation was successful and enhanced the PDT activities of the dyes MCF-7 cancer cells in vitro from 48.2 to 29.6 μM for 5 and 5-FA, and from 43.9 to 13.3 μM for 6 and 6-FA. Relatively high dark toxicity was observed for 6-FA of 26.1 μM. When the nitrogen atoms of the meso-pyridyl rings were quaternized (5-FAQ and 6-FAQ) to further enhance the aqueous solubility of the complexes, it was not possible to calculate an IC50 value. When octanol-water partition coefficients (Log P) were calculated by the shake flask method, values of −0.70 and −1.70 were obtained for 5-FAQ and 6-FAQ, respectively. This provides evidence that the dyes are too water-soluble and not sufficiently lipophilic. The PACT activity properties of the synthesised diiodinated aza-BODIPYs were studied against Staphylococcus aureus (S. aureus) through photoirradiation for 60 min with Thorlabs M660L4 (280 mW.cm−2) and M730L4 (160 mW.cm−2) light emitting diodes (LEDs) mounted on the illumination chamber of Modulight® 7710-680 medical laser system providing doses at the well-plate of 100 and 57 J.cm−2.min−1. Aza- BODIPYs 2, 3 and 4 all inhibited the growth of S. aureus but with relatively low Log10 reductions of 1.37, 1.20 and 0.20. In contrast, aza-BODIPY 1 was found to have a Log10 reduction of 7.82. The PACT activities of free base and Sn(IV) 5-[4-(3- bromoethylcarboxyamidyl)phenyl]-10,15,20-triphenylporphyrins (7 and 8) prepared by Dr Balaji Babu (New Journal of Chemistry 2022, 46, 5288-5295) were tested against S. aureus to determine whether adding a triphenylphosphonium moiety to form free base and Sn(IV) 5-[4-(triphenylphosphonium)ethylcarboxyamidyl)phenyl]-10,15,20- triphenylporphyrin (18 and 19) enhances the photo-induced antibacterial activity, in addition to optimising the PDT properties due to its mitochondria-targeting properties. The PACT activities obtained against S. aureus were not favourable, but 18 exhibited enhanced activity across the studied concentration range. The potential utility of aza-BODIPY dyes 1-4 and their non-iodinated analogues (1a- 4a) for optical limiting applications was analysed by carrying out a series of Z-scan measurements, since dyes of this type have large ground state dipole moments, and this can enhance the non-linear optical limiting response. All the aza-BODIPY dyes under investigation exhibited intense non-linear absorption (NLA) behaviour with Zscan profiles that contain significant reverse saturable absorption (RSA) responses. Aza-BODIPYs 1, 2a, 2, 3, 4a, and 4 decreased the transmitted intensity of the strong laser beam to less than 50% of the linear response in organic solutions with a fixed absorbance of 1.8 for the main aza-BODIPY spectral band and a laser pulse input energy of 42 μJ. Higher second-order hyperpolarizability (γ) values were obtained for iodinated dyes 1, 2, 3 and 4. The highest value of 3.15×10−29 esu was obtained for 1. A comparative study involving the four non-iodinated dyes 1, 2, 3 and 4 and seven 1,3,5,7-tetraaryl aza-BODIPY dyes reported previously in the PhD thesis of Gugu Kubheka at Rhodes University demonstrated that there was no clear trend correlation between the γ values calculated from the Z-scan measurements and calculated dipole moments. , Thesis (PhD) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-10-11

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Photodynamic anticancer and antimicrobial activities of novel bacteriochlorins

- Tauyakhale, Kaisano Goodness

Authors: Tauyakhale, Kaisano Goodness
Date: 2024-10-11
Subjects: Uncatalogued
Language: English
Type: Academic theses , Master's theses , text
Identifier: http://hdl.handle.net/10962/464587 , vital:76524
Description: The World Health Organization cautioned that the major contributing factors of cancer amongst people are the excessive usage of alcohol, smoking, lack of exercise and low intake of fruits, vegetables, and high-fibre foods. Furthermore, cancer by far is reported to be the most common and leading cause of death worldwide (1 in 6 deaths is due to cancer). Moreover, it is reported that cancer kills more people than tuberculosis, malaria and AIDS combined every year. Chemotherapy has been utilised as a mode of rehabilitation for complete being used in conjunction with surgery or to improve the state of well-being of patients until their point of death. However, it is well known for its adverse effects, such as loss of hair, altered gastric metabolism, vomiting and nausea, dehydration, weight loss, and loss of appetite. For this reason, photodynamic therapy (PDT) was developed as an alternative. A molecular dye (photosensitiser/PS) and light of a specific wavelength produce cytotoxic singlet oxygen species, which induce cell death. The aim of this project is to prepare novel structurally modified porphyrin-type dyes that absorb far into the near-infrared region. Identifying suitable dyes that absorb significantly in the 700−800 nm region is particularly important from an African perspective, since melanin significantly limits the penetration of laser light into human tissue in the 600−700 nm region, where first- and second-generation photosensitiser dyes usually absorb. The porphyrin analogues that will be investigated in this regard are bacteriochlorins (BChls), which are known to have suitable optical properties that are potentially suitable in this regard. The first step of the study would be to synthesise tetraarylporphyrins with electron- withdrawing meso-aryl rings because their reduction to BChls is more readily attainable than is the case with electron-donating rings. However, these contrasting properties can be combined to tailor the BChls for effective photodynamic therapy, so the type of porphyrins synthesised will be tetraarylBChls with different meso-aryl groups to first analyze the induction of different chemical properties in this case, the impact of introducing electron donating (4- and 3-quinoline substituents) or electron-withdrawing (pentafluorophenyl substituents) groups on the meso-positions of the dyes and more specifically whether the position of the quinoline nitrogen atom relative to the core of the BChl has any significant impact on the reactivity of the dye (the 4- or 3-position of the quinoline). The next factor to be considered is the induction of the heavy atom effect by introducing a metal in the centre of the dye in order to try to increase the singlet oxygen quantum yields for high production of reactive oxygen species and singlet oxygen and further red shift the lowest energy absorption band of the BChls in the therapeutic window for deep tissue penetration for effective. Lastly, the goal will be to explore whether the delivery of bacteriochlorin photosensitisers to cancer cells can be enhanced by introducing quaternised nitrogen atoms to the meso-aryl ligands. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-10-11

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Selective and sensitive electrochemical detection of the Human Epidermal Growth Receptor 2 breast cancer biomarker, using Co (II) phthalocyanine-nanoparticle based platforms

- Centane, Sixolile Sibongiseni

Authors: Centane, Sixolile Sibongiseni
Date: 2024-10-11
Subjects: Uncatalogued
Language: English
Type: Academic theses , Doctoral theses , text
Identifier: http://hdl.handle.net/10962/466569 , vital:76753 , DOI https://doi.org/10.21504/10962/466570
Description: Breast cancer is the world’s leading cause of cancer related deaths in women worldwide. The main reason lies in its late detection, mostly in the metastatic stage resulting in poor after-therapy prognosis, despite advances in methods of diagnosis and therapy. The reason for late-stage detection, is because breast cancer like any other cancers is asymptomatic in its early stages. Significant and characterizable features present in the later stages. Furthermore, conventional methods for breast cancer detection are more useful in the identification of the phenotypic features of cancer cells that arise at a later stage of the disease. Another issue with conventional methods where cancer diagnosis is concerned is that they tend to be specialist-dependent, time consuming and costly. Thus, easy, fast and inexpensive detection methods need to be developed urgently. Biomarker-based cancer diagnosis has emerged as one of the most promising strategies for early diagnosis, monitoring disease progression, and subsequent cancer treatment. This thesis focuses on the design and development of novel electrochemical biosensor platforms towards the low cost, efficient, sensitive and simple detection of early-stage breast cancer biomarker, human epidermal growth factor 2 (HER2). The electrochemical method is preferred because of its moderate cost, rapid response, ease of operation, readily quantifiable signal as well as high sensitivity and selectivity with lower detection limits. This thesis reports on two strategies towards signal amplification and sensitive detection of HER2, namely signal based amplification and target-based amplification. The former focuses on electrode or transducer modification techniques for improved signal to noise ratio. In which case; novel nanocomposites of phthalocyanines, graphene quantum dots, gold nanoparticles and cerium oxide nanoparticles are used for electrode modification for signal amplification and biorecognition element immobilization. The biorecognition elements of choice, are an aptamer and antibody known to be specific to the HER2 antigen for an enhanced sensor sensitivity and specificity. The second strategy focuses on increasing the number of detectable targets on the electrode surface towards enhanced sensitivity, precision and sensor accuracy. In which case; the performance of the aptamer and the antibody as recognition elements was explored. Furthermore, the effect of arrangement of these recognition elements on the electrode surface is investigated and reported upon. The strategies covered in this thesis are expected to result in novel biosensor platforms that can detect the HER2 biomarker with high precision, reproducibility, sensitivity and stability; towards low cost and effective early-stage breast cancer diagnostic tools. , Thesis (PhD) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-10-11

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The effect of an alkyl chain and β-diketonato-metal moiety on the photochromic behaviour of azobenzene compounds as materials for solar thermal fuels

- Bokhe, Witness Londi

Authors: Bokhe, Witness Londi
Date: 2024-10-11
Subjects: Photochemistry , Isomerization , Solar thermal energy , Solar thermal fuel , Liquid crystals , Optical materials
Language: English
Type: Academic theses , Master's theses , text
Identifier: http://hdl.handle.net/10962/464510 , vital:76517
Description: Scientists have been studying the development of renewable energy technologies in detail to create a sustainable energy supply. Among many new advanced material classes being researched recently are photo functional and photo responsive materials. These classes include azobenzene derivatives which are characterized by azo linkage (N=N) sandwiched by two phenyl rings. The trans-to-cis isomerization of azobenzene is a highly efficient and reversible process, making it an ideal candidate for solar thermal energy storage. This research investigates the impact of alkyl chain modifications and the incorporation of a β-diketonato-copper(II) complex on azobenzene derivatives, aiming to optimize their performance as efficient components in solar thermal fuel cells (STFs). The study focuses on a comprehensive analysis of these materials' ability to capture, convert, store, and release solar energy for enhanced sustainability in renewable energy applications. Experimental methodologies include synthesis of azobenzene derivatives with varying alkyl chain length, n (where n =8 & 10) and coordination of these compounds with a β-diketonato-copper(II) complex. Standard analytical techniques such as Nuclear Magnetic Resonance (1H and 13C NMR), Fourier Transform Infrared Spectroscopy (FTIR) and Ultraviolet/visible spectroscopy (UV/vis) were employed for chemical analysis of the synthesized material. Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), and Polarised Optical Microscope (POM) were used to study the thermal properties and morphology. The photostationery states were determined using NMR spectroscopy and the kinetic parameters of the cis-to-trans relaxation process determined by a UV spectroscopy study. The cis-to-trans isomerisation had a longer half-life than the trans-to-cis isomerisation. The band gap of the isomers is within the range of semiconducting inorganic materials. DSC and POM thermograms showed that the compounds are liquid crystalline. Finally, the study reports that the synthesised azobenzene derivatives show potential as material for solar thermal fuel cells because of their photo-isomerization ability. Furthermore, the synthesised compounds contribute to the advancement of sustainable and efficient solar energy utilization technologies, addressing the growing demand for clean energy solutions in the face of global environmental challenges. Because solar energy may be stored and used without causing direct emissions or pollution, they are considered clean energy. If solar thermal fuels fulfil sustainability standards, they may qualify as green energy. This entails minimising adverse effects on the environment, using non-toxic chemicals and procedures. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-10-11

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Graphene derivatives and electrocatalysts as composite electrodes for selective detection of catecholamine neurotransmitters

- Luhana, Charles Benjamin

Authors: Luhana, Charles Benjamin
Date: 2024-04-05
Subjects: Uncatalogued
Language: English
Type: Academic theses , Doctoral theses , text
Identifier: http://hdl.handle.net/10962/435907 , vital:73211 , DOI 10.21504/10962/435907
Description: In this thesis, we investigated the development of electrochemical sensing electrodes based on graphene derivatives and the electrocatalyst composites of metallophthalocyanines and metal oxides towards the selective and sensitive detection of catecholamine neurotransmitters (NTs). The graphene and its derivatives offer excellent electron conductivity and hence their use as base electrode materials. Metallophthalocyanines are N4-macrocyclic metal organic complexes that have structural modification flexible and 18-π electrons with excellent electrocatalytic properties. They can incorporate transition metal ions at the centre of the macrocycle ring, and this further enhances their electrocatalytic activity. Transition metal oxides are of interest as these also offer excellent redox properties and pH sensitivity. A pH sensitive electrochemical sensor based on aminated graphene quantum dots (AmGQDs) and cobalt tetra carboxyphenoxy phthalocyanine (CoTCPhOPc) covalent conjugates onto the pre-grafted isophthalic acid (IPA) gold electrode was fabricated. It displayed excellent analytical performance towards the detection of dopamine (DA), norepinephrine (NOR) and epinephrine (EP). The electrochemical sensor exhibited good ability to suppress the background current due to ascorbic acid (AA), a major interference in the detection catecholamine NTs. The carboxylic acid functional group of cobalt phthalocyanine induced the pH sensitivity of the thin film and electrostatic repulsion of the negatively charged ascorbate (AA-) anion at physiological pH. In addition, the electrode could screen-off biological molecules in the newborn calf serum as a representative of a real sample. An electrochemically reduced graphene oxide–based cobalt phthalocyanine polymer (polyCoTAPc) composite electrochemical sensor was fabricated on glassy carbon electrode, GCE-ERGO/polyCoTAPc. The GCE-ERGO/polyCoTAPc could detect dopamine and paracetamol simultaneously as co-existing analytes in buffer and synthetic urine samples. We observed, (i) very strong absorption of the materials, (ii) increase in the electrode surface area, (iii) excellent conductivity, and (iv) electrocatalytic activity of the ERGO/polyCoTAPc composite surface. Furthermore, a simple ultrasensitive electrochemical sensor based on nickel hydroxide thin film electrodeposited onto reduced graphene oxide-molybdenum disulfide (RGO/MoS2) composite resulted in the electrochemical sensor that can selectively and simultaneously detect ascorbic acid, dopamine, and uric acid. A distinct peak potential separation was observed with excellent electrocatalytic oxidation currents. The electrochemical sensors developed in this work exhibited high sensitivity, selectivity, stability, and low detection limits suitable for the detection and determination of catecholamine NTs. , Thesis (PhD) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-04-05

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Phthalocyanine-based bio-functional conjugates: photodynamic therapy and photoantimicrobial chemotherapeutic efficacy evaluation in-vitro

- Magadla, Aviwe

Authors: Magadla, Aviwe
Date: 2024-04-05
Subjects: Uncatalogued
Language: English
Type: Academic theses , Doctoral theses , text
Identifier: http://hdl.handle.net/10962/435918 , vital:73212 , DOI 10.21504/10962/435918
Description: This thesis reports on the syntheses and characterisation of symmetrical and asymmetrical phthalocyanines (Pcs) with different ring substituents derived to form either cationic styryl pyridine, cationic styryl pyridine triphenylphosphonium (TPP+)-based, benzothiazole, cationic pyridyl-dihydrothiazole and other closely related groups. The starting Pc complex of the synthesised Pc derivatives was typically obtained through the cyclotetramerisation of a substituted phthalonitrile. Then, depending on the desired final complex, the desired complexes were synthesised through the Knoevenagel condensation, alkylation reaction, and Schiff base reaction. Furthermore, silica nanoparticles (SiNPs) were also used to encapsulate Pcs. Following aminopropyl triethoxysilane amino (APTES) functionalisation of the surface of the Pc@SiNPs-APTES, biomolecules such as gallic acid, folic acid, and ampicillin were covalently attached to the surface. Additionally, Pc@SiNPs-APTES is protonated with 1,3-propanesultone. The pair of synthesised asymmetric Pcs is attached to ciprofloxacin (CIP) via an amide bond. Different analytical methods were used to characterise the Pcs and their conjugates. The photophysics and photochemistry of the Pcs both by themselves and in their conjugate form when doped with SiNPs. The cationic Pcs were able to produce sufficient singlet oxygen on their own in most cases. This is explained by the Pcs greater solubility in water. Since singlet oxygen is produced from the triplet state, singlet oxygen quantum yield (Δ) values complement triplet quantum yield (T) values. Low Δ values could be attributed to ineffective energy transfer; screening effects may have prevented the excited triplet state of the Pcs from interacting with the ground state molecular oxygen, lowering the Δ values. In other instances, the Pcs' protection by the SiNPs could be credited with extending the triplet lifetime. The direct connection of Pcs with CIP increased the formation of T and Δ in ABSTRACT comparison to Pcs alone. Both in planktonic and biofilm form, the cationic Pcs and conjugates showed enhanced bacterial elimination. The Pcs and conjugates demonstrated significant activity in photodynamic therapy treatment (PDT) experiments at the tested doses. In both PDT and photodynamic antimicrobial chemotherapy (PACT) treatment, the cationic Pcs outperformed the neutral Pc in terms of biological activity. , Thesis (PhD) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-04-05

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Aptamer-based biosensor for prostate specific antigen detection using cobalt phthalocyanine-exfoliated graphite composites

- Benise, Emihle

Authors: Benise, Emihle
Date: 2024-04-04
Subjects: Aptamer , Exfoliated graphite nano-platelets , Phthalocyanines , Impedance spectroscopy , Prostate-specific antigen
Language: English
Type: Academic theses , Master's theses , text
Identifier: http://hdl.handle.net/10962/434850 , vital:73110
Description: The work focuses on the development of biosensors and their use for the detection of prostate specific antigen (PSA). Four cobalt phthalocyanines (CoPcs) complexes: (1) cobalt tetra pyridyloxy phthalocyanine, (2) cobalt tetra acetamidophenoxy phthalocyanine, (3) cobalt tris(acetamidophenoxy) mono benzoic acid phthalocyanine, and (4) cobalt tris(acetamidophenoxy) mono propionic acid phthalocyanine, an exfoliated graphite (EG), and aptamer are used to make probes for PSA detection. Each complex is π-π stacked onto the EG to form EG-CoPc(π-π) hybrid which was used to modify a glassy carbon electrode (GCE). EG and CoPc were also used to modify the GCE sequential (seq) with CoPc on top to give GCE-EG-CoPc(seq). For the detection PSA, PSA specific aptamer was either sequential added or covalently linked to complexes 3 and 4 on the modified electrodes and was only sequentially added onto complexes 1 and 2 modified electrodes. Electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV) were the techniques used for the detection of PSA. The electrodes were found to be selective in bovine serum albumin, glucose and cysteine and stable when 50 DPV scans were run. Electrodes gave good % recovery when human serum was spiked with different PSA concentrations. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-04-04

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Insights: elucidation of squalene monooxygenase inhibitors for lowering cholesterol in cardiovascular diseases

- Leoma, Mofeli Benedict

Authors: Leoma, Mofeli Benedict
Date: 2024-04-04
Subjects: Uncatalogued
Language: English
Type: Academic theses , Master's theses , text
Identifier: http://hdl.handle.net/10962/434861 , vital:73111
Description: Statins have been used to lower high cholesterol levels in the past few decades. However, several studies have shown that some people taking statins experience side effects over time, especially elderly patients, women of childbirth possibility, and children. Several studies have shown that the majority of people with underlying cardiovascular complications caused by high cholesterol are at a greater risk of fatality due to COVID-19, regardless of age and sex. The literature suggests that antimycotic squalene monooxygenase inhibitors, terbinafine and its derivatives, and anticholesterolemic squalene monooxygenase (SM) inhibitors could be another option and a safer remedy for lowering cholesterol in mammals. Molecular docking calculations, molecular dynamics (MD) simulations, molecular mechanics generalized born surface area (MM-GBSA) calculations, quantum mechanics/molecular mechanics calculations (QM/MM), and density functional theory (DFT) calculations were used in this study. An early stage in drug discovery, in which small molecular hits from high- throughput screening (HTS) are evaluated and undergo limited optimization to identify promising lead compounds, is referred to as lead generation. To address the first step of lead generation, the number of compounds to be tested was narrowed down, and the hit compounds that could be taken for further tests were obtained. Thus, the molecular docking technique was taken advantage of, which assisted us in identifying the antimycotic ligand SDZ 18, which had a good binding affinity of about -8,4 kcal mol−1. Another widely employed strategy, the molecular mechanics-generalized born surface area (MM-GBSA), was used to investigate the binding free energies of the protein-ligand complexes to validate the binding affinities obtained from molecular docking. Despite the excellent docking results, it must be emphasized that the stability of the ligand in the binding pocket must be investigated. To address this, the protein-ligand complexes were then taken through molecular dynamics for 100 ns simulations calculations which showed that the inhibitors stayed in the binding pocket with the RMSD values below 3.5 Å for most systems. This provided insight into a realistic model because the docked complexes were placed in conditions closer to the physiological environment at 300 K and 1.01325 bar, and in an explicitly solvated dynamic environment. Density functional theory (DFT) at the B3LPY level of theory using the standard 6-31G(d,p) basis set was used to assess the reactivity and other properties of the SM inhibitors. ONIOM calculations were performed to explain what was happening at the microscopic level by calculating the total energy of the complex. The aim of this project was to efficiently uncover the non-physical aspects of SM inhibitors with the help of computational techniques to identify new drugs that can lower high cholesterol levels. From a theoretical perspective, the results obtained from docking indicated that the antimycotic ligands SDZ SBA 586 18 and TNSA 84 (trisnor-squalene alcohol ) have good binding affinities, and the MM-GBSA method provided free energy calculations. MD results indicated that the stability of the ligand in the binding pocket was achieved during the 100 ns simulations. The HOMO-LUMO energy gaps obtained from DFT calculations provided information on the reactivity of the ligands. Other insights into the protein-ligand complexes were obtained from a hybrid ONIOM QM/MM study. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
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Date Issued: 2024-04-04

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Asymmetrical zinc(II) phthalocyanines conjugated to nanomaterials for degradation of organic pollutants and inactivation of Staphylococcus aureus bacteria

- Mgidlana, Sithi

Authors: Mgidlana, Sithi
Date: 2023-10-13
Subjects: Uncatalogued
Language: English
Type: Academic theses , Doctoral theses , text
Identifier: http://hdl.handle.net/10962/431859 , vital:72809 , DOI 10.21504/10962/431860
Description: This thesis reports on the syntheses and characterization of asymmetrical phthalocyanines (Pcs) with different ring substituents (tert-butyl, ester, diimide, trimethoxy, acetophenone, heptanoylphenoxy, perfluorophenoxy, dimethoxy, propanoic acid, acetic acid, carboxylic acid, aminophenoxy, acrylic acid). Several nanoparticles including metal tungstate, capped with glutathione and 1-mercaptohexanol are prepared and characterized using analytical techniques. The synthesized Pcs are covalently linked to various nanoparticles (NPs) through ester and amide bonds to form Pc-NP conjugates, in order to improve their catalytic properties. The Pcs and their conjugates are characterized using different analytical techniques. The photophysics and photochemistry of the MPcs and conjugates are studied. The conjugates T). The complexes and the conjugates with nanomaterials are evaluated for singlet oxygen-generating ability. Conjugates generate higher singlet oxygen in comparison to Pc complexes alone. The photocatalytic activity of the conjugates of ZnPc complexes with NiWO4, Ag2WO4, Bi2WO6, CoWO4, and Ag-Fe3O4-based nanoparticles is evaluated based on photodegradation of methylene blue, tetracycline, and dibenzothiophene. The photocatalytic efficiencies of the synthesized phthalocyanine complexes increased in the presence of nanoparticles. This work also reports on the photodynamic antimicrobial chemotherapy activity of these materials against Staphylococcus aureus (S. aureus) bacteria in DMSO. The results indicated that silver-based nanoconjugates exhibit high antimicrobial activity with high log reductions compared to NiWO4, CoWO4, and Ag-Fe3O4-based materials. The z-scan technique is employed to experimentally test the nonlinear optical response of complexes and nanoconjugates in solution. The nonlinear absorption coefficient, third-order optical susceptibility and optical limiting threshold of the materials are obtained from the Z-scan aperture data. The nonlinear absorption parameters improved in the presence of semiconductor quantum dots, with 1-ethanoic-CdTe/ZnSeS/ZnO giving the best results due to the presence of electron-donating substituents. , Thesis (PhD) -- Faculty of Science, Chemistry, 2023
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Date Issued: 2023-10-13

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Enhancement of the electrocatalytic activity of phthalocyanines through the reduction in symmetry and conjugation to detonation nanodiamonds

- Ncwane, Lunathi

Authors: Ncwane, Lunathi
Date: 2023-10-13
Subjects: Phthalocyanines , Electrocatalysis , Nanodiamonds , Hydrazine
Language: English
Type: Academic theses , Master's theses , text
Identifier: http://hdl.handle.net/10962/424541 , vital:72162
Description: This thesis reports on the synthesis of novel phthalocynines tetrakis[(benzo[d]thiazol-2ylthio)phthalocyaninato]cobalt(II)chloride (complex 1) and tris(2-(ethylthio)benzo[d]thiazole)2-(phthalocyanine-9-ylthio)propionate cobalt(II) chloride (complex 2). The complexes are combined with DNDs via different techniques such as π-π stacking, covalent linkage and sequential modification on glassy carbon electrode. The synthesized MPcs and conjugates were characterized using UV-visible, mass, Fourier transform infrared, and Raman spectroscopies as well as transmission electron microscopy and dynamic light scattering. Combining MPcs with DNDs sought to improve electrooxidation of hydrazine. The electrochemical studies were conducted using cyclic voltammetry, chronocoloumetry, electrochemical impedance spectroscopy and chronoamperometry. Hydrazine was utilized as an analyte of interest, due to its mutagenic and carcinogenic effects. Glassy carbon electrodes (GCE) were modified using drop and dry method. The conjugation via covalent linkage proved to be the best way of enhancing electrocatalytic properties. Since it performed better in terms of limit of detection (0.33 μM), even though catalytic rate and sensitivity are not the highest. , Thesis (MSc) -- Faculty of Science, Chemistry, 2023
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Date Issued: 2023-10-13

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