The photocatalytic properties of zinc phthalocyanines supported on hematite nanofibers for use against methyl orange and Staphylococcus aureus
- Authors: Mapukata, Sivuyisiwe , Britton, Jonathan , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230184 , vital:49751 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113637"
- Description: Heterogeneous photocatalysis is a promising approach for environmental remediation from contaminants including microorganisms and organic pollutants. In this work, hematite nanofibers are fabricated and modified with a novel monosubstituted Pc (4) as well as an asymmetrical tetrasubstituted Pc (5) with the aim of creating hybrid photocatalysts. The photocatalytic activities of the unmodified and phthalocyanine modified hematite nanofibers were compared based on their efficiencies in the photoinactivation of S. aureus and photooxidation of methyl orange. For both applications, the hybrid nanofibers were found to be more efficient photocatalysts than the unmodified hematite nanofibers. Comparison of the modified nanofibers (4-Fe2O3 and 5-Fe2O3) showed that they have comparable antibacterial activity while the 5-Fe2O3 nanofibers are the best for the photooxidation of methyl orange. The singlet oxygen generation efficiency, high activity, versatility, regenerability and thus reusability of the fabricated hybrid nanofibers makes them ideal candidates for real life water treatment studies.
- Full Text:
- Date Issued: 2022
Folic acid-modified phthalocyanine-nanozyme loaded liposomes for targeted photodynamic therapy
- Authors: Nwahara, Nnamdi , Abrahams, Garth , Prinsloo, Earl , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231369 , vital:49881 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102527"
- Description: The hypoxic tumour microenvironment and poor spatiotemporal localization of photosensitizers are two significant obstacles that limit practical applications of photodynamic therapy. In response, a biocompatible, light-activatable liposome integrated with both a zinc phthalocyanine photodynamic component and Pt nanoparticles-decorated with MnO2 catalase-mimicking component are engineered. This multifunctional system was rationally designed using unsaturated phospholipids to achieve on-demand drug release following light irradiation. Specificity was achieved by folic acid functionalization resulting in folate-modified liposomes (FTLiposomes). We demonstrated its specific uptake by fluorescence imaging using folate receptor (FR) overexpressing HeLa and MCF-7 cells as in vitro models. This multifunctional liposome exhibits superior hypoxic anti-tumour effects and holds the potential to reduce side effects associated with untargeted therapy. Fluorescence of the constituent ZnPc and folate-receptor targeting could enable tracking and permit spatiotemporal regulation for improved cancer treatment.
- Full Text:
- Date Issued: 2021
Nanohybrid electrocatalyst based on cobalt phthalocyanine-carbon nanotube-reduced graphene oxide for ultrasensitive detection of glucose in human saliva
- Authors: Adeniyi, Omotayo , Nwahara, Nnamdi , Mwanza, Daniel , Nyokong, Tebello , Mashazi, Philani N
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231356 , vital:49880 , xlink:href="https://doi.org/10.1016/j.snb.2021.130723"
- Description: The current diabetes management systems require collecting blood samples via an invasive and painful finger pricking leading to the formation of callus, scarring and loss of sensibility to patients due to continuous monitoring. Therefore, a non-invasive and painless method of determining glucose levels would be desirable to diabetes patients who need constant monitoring. Saliva glucose measurement is a non-invasive alternative for diabetes management. A highly sensitive, stable, and selective non-enzymatic electrochemical sensor that can accurately quantify saliva glucose is required. A single-walled carbon nanotube/reduced graphene oxide/cobalt phthalocyanines nanohybrid modified glassy carbon electrode (GCE-SWCNT/rGO/CoPc) has been fabricated for the non-enzymatic determination of glucose in human saliva. The SWCNT/rGO/CoPc was characterized using various spectroscopic, microscopic, and electrochemical techniques. The synergistic effect between SWCNT, rGO, and CoPc facilitated excellent electron transfer process that improved the sensor sensitivity. The GCE-SWCNT/rGO/CoPc sensor exhibited two linear responses in the 0.30 μM to 0.50 mM and 0.50–5.0 mM glucose concentration ranges, and the detection limit was 0.12 μM. The sensor had an excellent saliva glucose detection sensitivity of 992.4 μA·mM−1·cm−2 and high specificity for glucose in the presence of other coexisting analytes. In addition, it showed good storage stability, reusability, and a fast response time of about 1.2 s. The GCE-SWCNT/rGO/CoPc nanohybrid electrode showed excellent potential for developing accurate, non-invasive, and painless glucose sensing.
- Full Text:
- Date Issued: 2021
Photocatalytic desulfurization of dibenzothiophene using methoxy substituted asymmetrical zinc (II) phthalocyanines conjugated to metal tungstate nanomaterials
- Authors: Mgidlana, Sithi , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185760 , vital:44421 , xlink:href="https://doi.org/10.1016/j.poly.2021.115053"
- Description: We report on the syntheses of three asymmetrical zinc(II) phthalocyanine endowed with benzoic acid, phenylpropanoic acid, and phenylacetic acid units: (1), (2), and (3), respectively. Metal tungstate nanoparticles, capped with glutathione were prepared and characterized using analytical techniques. Complexes were covalently linked to nickel tungstate (NiWO4) and bismuth tungstate (Bi2WO6) through an amide bond. The complexes and the conjugates with nanomaterial were evaluated for singlet oxygen generating ability. Complexes 1–2 and their conjugates generate higher singlet oxygen compared to 3 and its corresponding conjugates. The conjugates show degradation of dibenzothiophene (DBT) in fuel with shorter half-lives and greater initial rate values compared to phthalocyanines alone.
- Full Text:
- Date Issued: 2021
Visible light responsive TiO2-graphene oxide nanosheets-Zn phthalocyanine ternary heterojunction assisted photoelectrocatalytic degradation of Orange G
- Authors: Nwahara, Nnamdi , Adeniyi, Omotayo , Mashazi, Philani N , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185446 , vital:44387 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113291"
- Description: Herein, we report on the successful fabrication of a visible light-responsive TiO2 - graphene oxide nanosheets – Zn phthalocyanine (TiO2@GONS@ZnPc) ternary structure for the photoelectrochemical degradation of Orange G azo dye. The characterization of TiO2@GONS@ZnPc composite was achieved using various spectroscopic and microscopic techniques. Our results show that the TiO2@GONS@ZnPc surface hybrid heterojunction promotes charge separation and electron migration, significantly improving the degradation efficiency with an applied potential. For the first time, we show the existence of a non-radical activation route for persulfate (PS) using such π electron-rich ZnPc-GONS catalysts. The degradation kinetics were found to follow pseudo first order kinetics. Electron spin resonance analyses suggested that neither hydroxyl radicals nor sulfate radicals were produced therein, and therefore were not responsible for the persulfate-driven oxidation of the OG dye. These findings suggest that both which GONS and ZnPc play a critical role in mediating the eventual charge transfer mediated PS activation. The results illustrate the remarkable capacity of the TiO2@GONS@ZnPc composite to rapidly degrade Orange G by a coupled TiO2@GONS@ZnPc-persulfate system.
- Full Text:
- Date Issued: 2021
The photodynamic antimicrobial chemotherapy of Stapphylococcus aureus using an asymmetrical zinc phthalocyanine conjugated to silver and iron oxide based nanoparticles
- Authors: Mapukata, Sivuyisiwe , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186078 , vital:44461 , xlink:href="https://doi.org/10.1016/j.jphotochem.2020.112813"
- Description: The synthesis and characterisation of asymmetrical zinc(II) 2(3)-mono-isophthalic acid-9(10),16(17),23 (24)-tri (tert-butylphenoxy) phthalocyanine (complex 4) are reported. The phthalocyanine is conjugated to cysteamine capped silver nanoparticles (Cys-Ag NPs), amine functionalised iron oxide magnetic nanoparticles (NH2-Fe3O4 NPs) and a core-shell composite of the two (Cys-Fe3O4@Ag) via amide bonds. The photo-physico-chemical properties of complex 4 and its respective nanoconjugates (4-Ag, 4-Fe3O4 NPs and 4-Fe3O4@Ag NPs) are also reported. The nanoconjugates showed improved triplet and singlet oxygen quantum yields compared to complex 4. The antibacterial activity of complex 4 and its nanoconjugates were also evaluated on S. aureus wherein their activity was found to be mainly visible light driven with the best catalyst being 4-Fe3O4@Ag. The work therefore demonstrates the feasibility of phthalocyanine-nanoparticle based compounds as potential agents in real life antibacterial treatment
- Full Text:
- Date Issued: 2020
Photophysicochemical properties and surface-enhanced Raman scattering of phthalocyanine-nanoparticle conjugates
- Authors: Nwahara, Nnamdi
- Date: 2019
- Subjects: Boron compounds , Electrochemistry , Phthalocyanines , Nanoparticles , Bioconjugates , Raman effect
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/71647 , vital:29928
- Description: This work presents the synthesis, photophysical and photochemical characterization of a series of metallophthalocyanines (MPcs) and boron dipyrromethene (BODIPY) and their conjugates with either gold or silver nanoparticles (AuNPs or AgNPs) or graphene quantum dots (GQDs). The rich π-electron systems of GQDs and MPcs employed in this work enabled the coordination of MPcs to GQDs (either as pristine or modified) via the non-covalent (π-π stacking) method. GQDs, AuNPs and AgNPs were also functionalized with L-glutathione (GSH) in order to assist coupling to the Pcs or BODIPY dye. Spectroscopic and microscopic studies confirmed the formation of the respective nanoparticles (NPs) as well as the conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines (Pcs) or BODIPY alone. This work also shows that the incorporation of folic acid (FA) into Pcs-NPs composites leads to further enhancements in the singlet oxygen generation capabilities of the resulting conjugates, and so experimentally demonstrates for the first time, a synergy between FA and the respective nanoparticles (GQDs, AuNPs and AgNPs) in affecting the photophysical properties of Pcs complexes. GQDs and Pcs/GQDs hybrids were also herein decorated with AuNPs – metallic nanostructures that employ localized surface plasmon resonances to capture or radiate electromagnetic waves at optical frequencies. These nanostructures herein reported, have been shown to possess enhanced light-matter properties, enabling unique surface-enhanced Raman scattering (SERS) behaviours, with unprecedented enhancement factors of up to 30-fold. This work therefore, reports on the fabrication of Pc/GQDs/AuNPs hybrids and experimentally demonstrates their incredible potential as novel Raman-active PDT agents.
- Full Text:
- Date Issued: 2019
In-situ synthesis of gold nanoparticles on graphene quantum dots-phthalocyanine nanoplatforms: First description of the photophysical and surface enhanced Raman scattering behaviour
- Authors: Nwahara, Nnamdi , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187638 , vital:44682 , xlink:href="https://doi.org/10.1016/j.jphotochem.2018.04.011"
- Description: Owing to the need for new low-dimensional molecular assemblies with tailored electronic properties, the current study presents a facile approach for the synthesis and assembly of gold nanoparticles (AuNPs) onto functional graphene quantum dots (GQDs)-phthalocyanines (Pcs) arrays and the investigation of their photophysical and surface enhanced Raman scattering (SERS) properties. The GQDs were functionalized with L-glutathione (GSH) (to form GQDs@GSH) in order to assist coupling to the low symmetry Zn tris–(tert–butyl) mono carboxyphenoxy (propionic acid) phthalocyanine (complex 1) to form 1@GQDs. The affinity of gold (Au) to sulphur (S) was exploited for the assembly of the AuNPs onto 1@GQDs platform to form 1@GQDs-AuNPs. Transmission electron microscopic investigations confirmed the formation of monodispersed, spherical Pc/GQDs@GSH/AuNPs hybrids. The nanocomposite displayed high triplet quantum yields, which translated into high singlet oxygen quantum yield as high as 87%. Furthermore, the formed composites demonstrated strong surface enhanced Raman scattering (SERS) properties with an unprecedented intrinsic maximal enhancement factor of more than 30-fold. These nanostructures also retain more than 90% of their original SERS intensities after a week of storage, displaying superb stability under ambient conditions. These results highlight the remarkable potential of this composite as a unique Raman-based PDT dosimetric agent.
- Full Text:
- Date Issued: 2018
In-situ synthesis of gold nanoparticles on graphene quantum dots-phthalocyanine nanoplatforms: First description of the photophysical and surface enhanced Raman scattering behaviour
- Authors: Nwahara, Nnamdi , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188183 , vital:44730 , xlink:href="https://doi.org/10.1016/j.jphotochem.2018.04.011"
- Description: Owing to the need for new low-dimensional molecular assemblies with tailored electronic properties, the current study presents a facile approach for the synthesis and assembly of gold nanoparticles (AuNPs) onto functional graphene quantum dots (GQDs)-phthalocyanines (Pcs) arrays and the investigation of their photophysical and surface enhanced Raman scattering (SERS) properties. The GQDs were functionalized with L-glutathione (GSH) (to form GQDs@GSH) in order to assist coupling to the low symmetry Zn tris–(tert–butyl) mono carboxyphenoxy (propionic acid) phthalocyanine (complex 1) to form 1@GQDs. The affinity of gold (Au) to sulphur (S) was exploited for the assembly of the AuNPs onto 1@GQDs platform to form 1@GQDs-AuNPs. Transmission electron microscopic investigations confirmed the formation of monodispersed, spherical Pc/GQDs@GSH/AuNPs hybrids. The nanocomposite displayed high triplet quantum yields, which translated into high singlet oxygen quantum yield as high as 87%. Furthermore, the formed composites demonstrated strong surface enhanced Raman scattering (SERS) properties with an unprecedented intrinsic maximal enhancement factor of more than 30-fold. These nanostructures also retain more than 90% of their original SERS intensities after a week of storage, displaying superb stability under ambient conditions. These results highlight the remarkable potential of this composite as a unique Raman-based PDT dosimetric agent.
- Full Text:
- Date Issued: 2018
Synthesis and photophysical properties of BODIPY-decorated graphene quantum dot–phthalocyanine conjugates
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
Wood preservation with gold hydroxyapatite system
- Authors: Ion, Rodica-Mariana , Nyokong, Tebello , Nwahara, Nnamdi , Suica-Bunghez, Ioana-Raluca , Iancu, Lorena , Teodorescu, Sofia , Dulama, Ioana D , Stirbescu, Raluca M , Gheboianu, Anca , Grigorescu, Ramona M
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187840 , vital:44702 , xlink:href="https://doi.org/10.1186/s40494-018-0202-5"
- Description: Over centuries, the external factors such as fire, low temperature, light or microbiological agents, act on the wood and induce some degradation processes, sometimes irreversible, identified by discoloration, fragility and unsightly appearance. Although there are numerous literature reports about different nanomaterials used for preservation and restoration of wood surfaces (calcium hydroxides, magnesium hydroxides, hydroxyapatite, or even organic resins as Paraloid B72), in this paper it is proposed a new system—gold hydroxyapatite (AuHAp), tested on the hazelnut wood samples (young and aged specimens), as a new solution for preservation of some wooden artifacts. This paper addresses a broad range of analytical methods: X-ray diffraction, UV–Vis spectrophotometry, Fourier transformed infrared spectroscopy, Raman spectroscopy, scanning electron microscopy with energy dispersive spectroscopy, chromatic parameters and hardness test. Also, humidity sorption/desorption measurements are used for humidity sorption and desorption evaluation. The adsorption and desorption tests determined the hydroscopic sorption properties of the wood specimens by measuring the mass of the specimens in equilibrium with air at a specific temperature and RH. All the results concluded that after the application of the new system on the hazelnut wood surface, a well distributed and uniform layer consisting from AuHAp systems with a network aspect are observed, which covers the wood vessels and fibers, filling the voids and stopping the wood weathering process, more accentuated at aged wood than at the young species.
- Full Text:
- Date Issued: 2018
Improving singlet oxygen generating abilities of phthalocyanines
- Authors: Nwahara, Nnamdi , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188943 , vital:44800 , xlink:href="https://doi.org/10.1080/00958972.2017.1313975"
- Description: Glutathione-capped graphene quantum dots (GQDs@GSH) were covalently linked to folic acid (FA). Aluminum tetrasulfonated phthalocyanine (ClAlTSPc) was then adsorbed on the GQDs@GSH-FA conjugate to form GQDs@GSH-FA/ClAlTSPc or on GQDs@GSH and pristine GQDs alone to form GQDs@GSH/ClAlTSPc and GQDs/ClAlTSPc, respectively. We report for the first time on the photophysicochemical behavior of the resulting nanoconjugates. The fluorescence quantum yields of pristine GQDs, GQDS@GSH, or GQDs@GSH-FA conjugate were quenched upon non-covalent interaction (π–π) with ClAlTSPc. There was an increase in triplet quantum yields from 0.38 for ClAlTSPc alone to 0.60, 0.75, and 0.73 when ClAlTSPc was linked to pristine GQDs, GQDs@GSH, and GQDs@GSH-FA, respectively. The singlet oxygen quantum yields also increased from 0.37 for ClAlTSPc alone to 0.42 (for ClALTSPc with pristine GQDs), 0.52 (for ClAlTSPc with GQDs@GSH), and 0.54 (for ClAlTSPc with GQDs@GSH-FA). Thus, the present work may lead to a new generation of carbon-based nanomaterial photodynamic therapy agents with overall performance superior to conventional agents in terms of singlet oxygen generation, water dispersibility, and biocompatibility.
- Full Text:
- Date Issued: 2017