The systematic assembly of prostate specific antigen electrochemical sensors based on asymmetric Co(II) phthalocyanines, graphitic quantum dots and an aptamer
- Authors: Nxele, Siphesihle Robin
- Date: 2022-04-08
- Subjects: Prostate-specific antigen , Electrochemical sensors , Phthalocyanines , Quantum dots , Co(II) phthalocyanines , Aptamer
- Language: English
- Type: Doctoral thesis , text
- Identifier: http://hdl.handle.net/10962/232893 , vital:50035 , DOI 10.21504/10962/232893
- Description: The need for low-cost, efficient and simple diagnostic tools has led to more research going into this subject, with the aim of making such medical devices more accessible where they are needed. This has led to more researchers developing point-of-care devices for this purpose worldwide, by sensor fabrication. This thesis focuses on electrochemical sensor development for the early diagnosis of prostate cancer. It is common knowledge that prostate cancer is one of the most prevalent carcinomas that have claimed lives due to late diagnosis where even the most invasive treatments have failed. For this reason, development of early detection devices that can even be used in the comfort of home is necessary and quite crucial. Electrochemical sensors have gained much attention due to their ease of fabrication, cost effectiveness, simplicity, ease of use and high efficiency. Using nanocomposites as modifiers has also become popular as they provide greater stability and improve detection limits when used together with biomolecules. With that said, the work reported herein has combined nanocomposites of graphenebased quantum dots, gold nanoparticles, phthalocyanines and an aptamer in order to fabricate aptasensors for the electrochemical detection of prostate cancer biomarker. The aptamer is specifically designed to bind to the biomarker, and the nanocomposites are expected to enhance current output thus lowering detection limits and increasing stability and efficiency. Reproducible results are also expected. Prior to the detection of the prostate cancer biomarker, the quantum dots-phthalocyanine nanohybrids were used to detect L-cysteine, which is an amino acid, in order to verify the synergistic effects as electrode modifiers that lead to the enhancement of current output. This increase in current output is then v exploited for the improvement of aptasensor functionality upon incorporation of the aptamer, for the detection of prostate specific antigen. The research in this thesis has been carried out with the intention of contributing to the world of medical research, more so because of the ever-increasing need for medical care to become accessible to all and not only to those who can afford expensive technologies and treatments. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-08
- Authors: Nxele, Siphesihle Robin
- Date: 2022-04-08
- Subjects: Prostate-specific antigen , Electrochemical sensors , Phthalocyanines , Quantum dots , Co(II) phthalocyanines , Aptamer
- Language: English
- Type: Doctoral thesis , text
- Identifier: http://hdl.handle.net/10962/232893 , vital:50035 , DOI 10.21504/10962/232893
- Description: The need for low-cost, efficient and simple diagnostic tools has led to more research going into this subject, with the aim of making such medical devices more accessible where they are needed. This has led to more researchers developing point-of-care devices for this purpose worldwide, by sensor fabrication. This thesis focuses on electrochemical sensor development for the early diagnosis of prostate cancer. It is common knowledge that prostate cancer is one of the most prevalent carcinomas that have claimed lives due to late diagnosis where even the most invasive treatments have failed. For this reason, development of early detection devices that can even be used in the comfort of home is necessary and quite crucial. Electrochemical sensors have gained much attention due to their ease of fabrication, cost effectiveness, simplicity, ease of use and high efficiency. Using nanocomposites as modifiers has also become popular as they provide greater stability and improve detection limits when used together with biomolecules. With that said, the work reported herein has combined nanocomposites of graphenebased quantum dots, gold nanoparticles, phthalocyanines and an aptamer in order to fabricate aptasensors for the electrochemical detection of prostate cancer biomarker. The aptamer is specifically designed to bind to the biomarker, and the nanocomposites are expected to enhance current output thus lowering detection limits and increasing stability and efficiency. Reproducible results are also expected. Prior to the detection of the prostate cancer biomarker, the quantum dots-phthalocyanine nanohybrids were used to detect L-cysteine, which is an amino acid, in order to verify the synergistic effects as electrode modifiers that lead to the enhancement of current output. This increase in current output is then v exploited for the improvement of aptasensor functionality upon incorporation of the aptamer, for the detection of prostate specific antigen. The research in this thesis has been carried out with the intention of contributing to the world of medical research, more so because of the ever-increasing need for medical care to become accessible to all and not only to those who can afford expensive technologies and treatments. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-08
The synergistic effects of coupling Au nanoparticles with an alkynyl Co (II) phthalocyanine on the detection of prostate specific antigen
- Nxele, Siphesihle Robin, Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Nxele, Siphesihle Robin , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230232 , vital:49756 , xlink:href="https://doi.org/10.1016/j.talanta.2021.122948"
- Description: Prostate specific antigen (PSA) aptasensors are fabricated using a novel asymmetrically substituted Co phthalocyanine (CoPc), gold nanoparticles (AuNPs) and PSA-specific antigen. The fabricated aptasensors are: GCE-AuNPs-Aptamer, GCE@CoPc-Aptamer and GCE-AuNPs@CoPc-Aptamer (GCE = glassy carbon electrode). The fabricated sensors are characterized at each modification step to monitor the changes occurring at the sensor surface. Concentration studies were carried out using differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) to determine detection limits. All the fabricated aptasensors were found to be highly specific and selective but the GCE-AuNPs@CoPc-Aptamer nanoconjugate performed the best. The aptasensors were also tested in spiked serum samples and detection limits, as well as % recoveries were determined. The results obtained showed that the GCE-AuNPs@CoPc-Aptamer has the potential to be used for clinical studies as the results agree with those obtained for detection of PSA in buffer.
- Full Text:
- Date Issued: 2022
- Authors: Nxele, Siphesihle Robin , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230232 , vital:49756 , xlink:href="https://doi.org/10.1016/j.talanta.2021.122948"
- Description: Prostate specific antigen (PSA) aptasensors are fabricated using a novel asymmetrically substituted Co phthalocyanine (CoPc), gold nanoparticles (AuNPs) and PSA-specific antigen. The fabricated aptasensors are: GCE-AuNPs-Aptamer, GCE@CoPc-Aptamer and GCE-AuNPs@CoPc-Aptamer (GCE = glassy carbon electrode). The fabricated sensors are characterized at each modification step to monitor the changes occurring at the sensor surface. Concentration studies were carried out using differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) to determine detection limits. All the fabricated aptasensors were found to be highly specific and selective but the GCE-AuNPs@CoPc-Aptamer nanoconjugate performed the best. The aptasensors were also tested in spiked serum samples and detection limits, as well as % recoveries were determined. The results obtained showed that the GCE-AuNPs@CoPc-Aptamer has the potential to be used for clinical studies as the results agree with those obtained for detection of PSA in buffer.
- Full Text:
- Date Issued: 2022
Time-dependent characterization of graphene quantum dots and graphitic carbon nitride quantum dots synthesized by hydrothermal methods
- Nxele, Siphesihle Robin, Nyokong, Tebello
- Authors: Nxele, Siphesihle Robin , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230917 , vital:49831 , xlink:href="https://doi.org/10.1016/j.diamond.2021.108751"
- Description: We report on the facile synthesis of graphene quantum dots (GQDs), nitrogen-doped quantum dots (NGQDs) and graphitic carbon nitride quantum dots (gCNQDs) by the bottom-up hydrothermal synthetic process. The time is varied to study its effects on the structural, hydrodynamic and optical properties of these nanostructures. The techniques used to characterize these nanostructures were transmission electron microscopy, X-ray diffractometry, dynamic light scattering, and zetametry (zeta potential), and by energy dispersive X-ray, UV/vis, fluorescence, Fourier transform infrared, Raman and X-ray photoelectron spectroscopies. For gCNQDs and NGQDs, Raman spectroscopy showed an increase in disorder with synthesis time, indicating introduction of more triazine groups for the former and increase in doping with the N atoms for the latter, hence higher temperatures are recommended. For GQDs, Raman spectra showed an increase in the spatial order of the π-conjugated structure with synthesis time. Considering all the techniques employed in this work, the synthesis times of 6h and 8 h are recommended for GQDs and NGQDs.
- Full Text:
- Date Issued: 2022
- Authors: Nxele, Siphesihle Robin , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230917 , vital:49831 , xlink:href="https://doi.org/10.1016/j.diamond.2021.108751"
- Description: We report on the facile synthesis of graphene quantum dots (GQDs), nitrogen-doped quantum dots (NGQDs) and graphitic carbon nitride quantum dots (gCNQDs) by the bottom-up hydrothermal synthetic process. The time is varied to study its effects on the structural, hydrodynamic and optical properties of these nanostructures. The techniques used to characterize these nanostructures were transmission electron microscopy, X-ray diffractometry, dynamic light scattering, and zetametry (zeta potential), and by energy dispersive X-ray, UV/vis, fluorescence, Fourier transform infrared, Raman and X-ray photoelectron spectroscopies. For gCNQDs and NGQDs, Raman spectroscopy showed an increase in disorder with synthesis time, indicating introduction of more triazine groups for the former and increase in doping with the N atoms for the latter, hence higher temperatures are recommended. For GQDs, Raman spectra showed an increase in the spatial order of the π-conjugated structure with synthesis time. Considering all the techniques employed in this work, the synthesis times of 6h and 8 h are recommended for GQDs and NGQDs.
- Full Text:
- Date Issued: 2022
Characterization of phthalocyanine functionalized quantum dots by dynamic light scattering, laser Doppler, and capillary electrophoresis
- Ramírez-García, Gonzalo, Oluwole, David O, Nxele, Siphesihle Robin, d’Orlyé, Fanny, Nyokong, Tebello, Bedioui, Fethi, Varenne, Anne
- Authors: Ramírez-García, Gonzalo , Oluwole, David O , Nxele, Siphesihle Robin , d’Orlyé, Fanny , Nyokong, Tebello , Bedioui, Fethi , Varenne, Anne
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238184 , vital:50595 , xlink:href="https://doi.org/10.1007/s00216-016-0120-x"
- Description: In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy.
- Full Text:
- Date Issued: 2017
- Authors: Ramírez-García, Gonzalo , Oluwole, David O , Nxele, Siphesihle Robin , d’Orlyé, Fanny , Nyokong, Tebello , Bedioui, Fethi , Varenne, Anne
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238184 , vital:50595 , xlink:href="https://doi.org/10.1007/s00216-016-0120-x"
- Description: In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy.
- Full Text:
- Date Issued: 2017
Electrode surface modification using iron(II) phthalocyanine immobilized via electrografting and click chemistry and clicked onto azide-functionalized quantum dots: applications in electrocatalysis
- Authors: Nxele, Siphesihle Robin
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3464 , vital:20501
- Description: Tetrakis(5-hexynoxy)Fe(II) phthalocyanine was used alone and in combination with quantum dots (QDs) in order to test the electrocatalytic ability with hydrazine and paraquat as the analytes of interest. This novel phthalocaynine was successfully synthesised and characterized using various characterisation techniques. The QDs used were the well-known core-shell CdSe/ZnS nanostructures. The fabrication of glassy carbon electrodes involved covalent attachment by electrochemical grafting and click chemistry for the first part of the work and the second part involved the conjugation of the synthesised QDs and the phthalocyanine by click chemistry. This approach of conjugating these nanostructures introduced another aspect of novelty to the work reported in this thesis. The immobilisation of this conjugate on a glassy carbon electrode (GCE) was achieved by adsorption. Characterisation techniques such as infrared spectroscopy, x-ray diffractometry, UV/vis spectroscopy, transmission electron microscopy and x-ray photoelectron spectroscopy were used to characterise the molecules and conjugates of interest. With respect to the electrocatalytic part of the work, electrode surface characterisation involved scanning electrochemical microscopy and cyclic voltammetry to determine changes in the nature of the surface as well as reactivity of the surface at different modification steps. Detection limits and the sensitivity determined for the electrocatalysts fabricated here proved to be an improvement compared to other reported work involving phthalocyanines and the test analytes chosen for application. With respect to the conjugate, the electrocatalytic ability was improved when the QDs and phthalocyanine were combined using click chemistry compared to using the phthalocyanine alone.
- Full Text:
- Date Issued: 2016
- Authors: Nxele, Siphesihle Robin
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3464 , vital:20501
- Description: Tetrakis(5-hexynoxy)Fe(II) phthalocyanine was used alone and in combination with quantum dots (QDs) in order to test the electrocatalytic ability with hydrazine and paraquat as the analytes of interest. This novel phthalocaynine was successfully synthesised and characterized using various characterisation techniques. The QDs used were the well-known core-shell CdSe/ZnS nanostructures. The fabrication of glassy carbon electrodes involved covalent attachment by electrochemical grafting and click chemistry for the first part of the work and the second part involved the conjugation of the synthesised QDs and the phthalocyanine by click chemistry. This approach of conjugating these nanostructures introduced another aspect of novelty to the work reported in this thesis. The immobilisation of this conjugate on a glassy carbon electrode (GCE) was achieved by adsorption. Characterisation techniques such as infrared spectroscopy, x-ray diffractometry, UV/vis spectroscopy, transmission electron microscopy and x-ray photoelectron spectroscopy were used to characterise the molecules and conjugates of interest. With respect to the electrocatalytic part of the work, electrode surface characterisation involved scanning electrochemical microscopy and cyclic voltammetry to determine changes in the nature of the surface as well as reactivity of the surface at different modification steps. Detection limits and the sensitivity determined for the electrocatalysts fabricated here proved to be an improvement compared to other reported work involving phthalocyanines and the test analytes chosen for application. With respect to the conjugate, the electrocatalytic ability was improved when the QDs and phthalocyanine were combined using click chemistry compared to using the phthalocyanine alone.
- Full Text:
- Date Issued: 2016
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