Enhanced Solar Efficiency via Incorporation of Plasmonic Gold Nanostructures in a Titanium Oxide/Eosin Y Dye-Sensitized Solar Cell
- Nyembe, Sanele, Chindeka, Francis, Ndlovu, Gebhu, Mkhohlakali, Andile, Nyokong, Tebello, Sikhwiyhilu, Lucy
- Authors: Nyembe, Sanele , Chindeka, Francis , Ndlovu, Gebhu , Mkhohlakali, Andile , Nyokong, Tebello , Sikhwiyhilu, Lucy
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295783 , vital:57377 , xlink:href="https://doi.org/10.3390/nano12101715"
- Description: Plasmonic gold nanoparticles significantly improved the efficiency of a TiO2 and Eosin Y based dye-sensitized solar cell from 2.4 to 6.43%. The gold nanoparticles’ sizes that were tested were 14 nm, 30 nm and 40 nm synthesized via the systematic reduction of citrate concentration using the Turkevich method. Prestine TiO2 without plasmonic gold nanoparticles yielded an efficiency of 2.4%. However, the loading of 40 nm gold nanoparticles into the TiO2 matrix yielded the highest DSSC efficiency of 6.43% compared to 30 nm (5.91%) and 14 nm (2.6%). The relatively high efficiency demonstrated by plasmonic gold nanoparticles is ascribed to light absorption/scattering, hot electron injection and plasmon-induced resonance energy transfer (PIRET), influenced by the size of the gold nanoparticles.
- Full Text:
- Date Issued: 2022
- Authors: Nyembe, Sanele , Chindeka, Francis , Ndlovu, Gebhu , Mkhohlakali, Andile , Nyokong, Tebello , Sikhwiyhilu, Lucy
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295783 , vital:57377 , xlink:href="https://doi.org/10.3390/nano12101715"
- Description: Plasmonic gold nanoparticles significantly improved the efficiency of a TiO2 and Eosin Y based dye-sensitized solar cell from 2.4 to 6.43%. The gold nanoparticles’ sizes that were tested were 14 nm, 30 nm and 40 nm synthesized via the systematic reduction of citrate concentration using the Turkevich method. Prestine TiO2 without plasmonic gold nanoparticles yielded an efficiency of 2.4%. However, the loading of 40 nm gold nanoparticles into the TiO2 matrix yielded the highest DSSC efficiency of 6.43% compared to 30 nm (5.91%) and 14 nm (2.6%). The relatively high efficiency demonstrated by plasmonic gold nanoparticles is ascribed to light absorption/scattering, hot electron injection and plasmon-induced resonance energy transfer (PIRET), influenced by the size of the gold nanoparticles.
- Full Text:
- Date Issued: 2022
Impedimetric aptasensor for HER2 biomarker using graphene quantum dots, polypyrrole and cobalt phthalocyanine modified electrodes
- Centane, Sixolile, Nyokong, Tebello
- Authors: Centane, Sixolile , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230960 , vital:49836 , xlink:href="https://doi.org/10.1016/j.sbsr.2021.100467"
- Description: A method is presented for the electrochemical detection of the breast cancer biomarker human epidermal growth factor receptor 2 (HER2). A glassy carbon electrode was modified using two techniques known as sequential adsorption and electro-polymerization, and the results are compared. The highly conductive polypyrrole (PPy) is used, in the presence of sulfur/nitrogen doped graphene quantum dots (SNGQDs) and a known cobalt phthalocyanine (CoPc). The different nanomaterials were used as an immobilization platform for the HER2 specific HB5 aptamer via amide linkage. The nanomaterials were arranged in various ways on the glassy carbon electrode, to investigate the effect of the electrode interface on the operational characteristics of a biosensor. The immobilized aptamer selectively recognizes HER2 on the electrode interface, and this leads to an increased charge transfer resistance (Rct) of the electrode when using ferricyanide as the electrochemical probe. The developed immunosensors showed high sensitivity with the best detection limit of 0.00141 ng/mL. The results showed that the method is simple and sensitive enough for the determination of HER2 in serum samples with good reproducibility and accuracy.
- Full Text:
- Date Issued: 2022
- Authors: Centane, Sixolile , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230960 , vital:49836 , xlink:href="https://doi.org/10.1016/j.sbsr.2021.100467"
- Description: A method is presented for the electrochemical detection of the breast cancer biomarker human epidermal growth factor receptor 2 (HER2). A glassy carbon electrode was modified using two techniques known as sequential adsorption and electro-polymerization, and the results are compared. The highly conductive polypyrrole (PPy) is used, in the presence of sulfur/nitrogen doped graphene quantum dots (SNGQDs) and a known cobalt phthalocyanine (CoPc). The different nanomaterials were used as an immobilization platform for the HER2 specific HB5 aptamer via amide linkage. The nanomaterials were arranged in various ways on the glassy carbon electrode, to investigate the effect of the electrode interface on the operational characteristics of a biosensor. The immobilized aptamer selectively recognizes HER2 on the electrode interface, and this leads to an increased charge transfer resistance (Rct) of the electrode when using ferricyanide as the electrochemical probe. The developed immunosensors showed high sensitivity with the best detection limit of 0.00141 ng/mL. The results showed that the method is simple and sensitive enough for the determination of HER2 in serum samples with good reproducibility and accuracy.
- Full Text:
- Date Issued: 2022
Integrated photocatalyst adsorbents based on porphyrin anchored to activated carbon granules for water treatment
- Oyim, James, Amuhaya, Edith K, Matshitse, Refilwe, Mack, John, Nyokong, Tebello
- Authors: Oyim, James , Amuhaya, Edith K , Matshitse, Refilwe , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300101 , vital:57893 , xlink:href="https://doi.org/10.1016/j.cartre.2022.100191"
- Description: Integration of adsorption and photocatalysis processes can lead to several benefits in water treatment. Integrating well-known adsorbents with photocatalysts ensures that all the interesting components are preserved and helps to overcome the serious downsides of each material and technique when operated independently. In this work, we introduce a new concept of combining both absorption and photodegradation mechanisms using organic photocatalytic adsorbents for water purification. This was achieved by formulating photosensitizing hybrids based on a newly synthesized chloroindium (III) 5,10,15,20-tetrakis(4-acetamidophenyl) porphyrin (InTAAP) compound, anchored on oxygen functionalized coconut shell-based activated carbon granules supports. The fashioned integrated photocatalyst adsorbent hybrid (InTAAP(ACO)) was then studied for their adsorption and photodegradation efficiency using methylene blue dye, where InTAAP(ACO) showed excellent photocatalytic activity compared to ACO and unfunctionalized activated carbon granules (AC), with appreciably high and adsorption properties as AC and ACO.
- Full Text:
- Date Issued: 2022
- Authors: Oyim, James , Amuhaya, Edith K , Matshitse, Refilwe , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300101 , vital:57893 , xlink:href="https://doi.org/10.1016/j.cartre.2022.100191"
- Description: Integration of adsorption and photocatalysis processes can lead to several benefits in water treatment. Integrating well-known adsorbents with photocatalysts ensures that all the interesting components are preserved and helps to overcome the serious downsides of each material and technique when operated independently. In this work, we introduce a new concept of combining both absorption and photodegradation mechanisms using organic photocatalytic adsorbents for water purification. This was achieved by formulating photosensitizing hybrids based on a newly synthesized chloroindium (III) 5,10,15,20-tetrakis(4-acetamidophenyl) porphyrin (InTAAP) compound, anchored on oxygen functionalized coconut shell-based activated carbon granules supports. The fashioned integrated photocatalyst adsorbent hybrid (InTAAP(ACO)) was then studied for their adsorption and photodegradation efficiency using methylene blue dye, where InTAAP(ACO) showed excellent photocatalytic activity compared to ACO and unfunctionalized activated carbon granules (AC), with appreciably high and adsorption properties as AC and ACO.
- Full Text:
- Date Issued: 2022
Disilane-bridged architectures with high optical transparency for optical limiting
- Feng, Hongjie, Zhou, Zhikuan, May, Aviwe K, Chen, Jiaying, Mack, John, Nyokong, Tebello, Gai, Lizhi, Lu, Hua
- Authors: Feng, Hongjie , Zhou, Zhikuan , May, Aviwe K , Chen, Jiaying , Mack, John , Nyokong, Tebello , Gai, Lizhi , Lu, Hua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190623 , vital:45011 , xlink:href="https://doi.org/10.1039/D1TC01488A"
- Description: A novel tetraphenylethylene (TPE) architecture that makes use of a disilane bridge was developed to successfully prepare organic optical power limiting (OPL) materials with high transparency. The σ-bridged TPE derivatives exhibit enhanced solid-state emission efficacies up to 4 times that of TPE. Due to the unique σ-electron delocalization, the incorporated Si–Si bridge gives rise to intense nonlinear optics (NLO) properties. These compounds show favorable optical transparency in the visible region, since the σ–π interaction has a relatively minor effect on the absorption properties of TPE. The poly(bisphenol A carbonate) (PBC) thin films of disilane-bridged compounds exhibit significant reverse saturable absorbance (RSA) responses during Z-scan measurements at 532 nm. In contrast, negligible OPL properties were observed in tetrahydrofuran (THF) solution and when a PBC thin film was prepared with TPE. The disilane-bridged molecular system represents a novel and easily prepared architecture for the construction of solid-state optical limiting materials.
- Full Text:
- Date Issued: 2021
- Authors: Feng, Hongjie , Zhou, Zhikuan , May, Aviwe K , Chen, Jiaying , Mack, John , Nyokong, Tebello , Gai, Lizhi , Lu, Hua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190623 , vital:45011 , xlink:href="https://doi.org/10.1039/D1TC01488A"
- Description: A novel tetraphenylethylene (TPE) architecture that makes use of a disilane bridge was developed to successfully prepare organic optical power limiting (OPL) materials with high transparency. The σ-bridged TPE derivatives exhibit enhanced solid-state emission efficacies up to 4 times that of TPE. Due to the unique σ-electron delocalization, the incorporated Si–Si bridge gives rise to intense nonlinear optics (NLO) properties. These compounds show favorable optical transparency in the visible region, since the σ–π interaction has a relatively minor effect on the absorption properties of TPE. The poly(bisphenol A carbonate) (PBC) thin films of disilane-bridged compounds exhibit significant reverse saturable absorbance (RSA) responses during Z-scan measurements at 532 nm. In contrast, negligible OPL properties were observed in tetrahydrofuran (THF) solution and when a PBC thin film was prepared with TPE. The disilane-bridged molecular system represents a novel and easily prepared architecture for the construction of solid-state optical limiting materials.
- Full Text:
- Date Issued: 2021
Electrochemical Detection of Nitrite on Electrodes Modified by Click Chemistry Using Asymmetrical Co (II) and Mn (III) Phthalocyanines Containing Push-Pull Substituents
- Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231425 , vital:49886 , xlink:href="https://doi.org/10.1149/1945-7111/ac377f"
- Description: The more conventional route to synthesizing asymmetric push-pull phthalocyanines (Pcs) involves pairing electron-donating substituents with electron-withdrawing groups in either an A3B or AB3 manner. In this work, a push-pull system fashioned from a substituent bearing different functional groups was created. Symmetric and asymmetric cobalt and manganese Pcs in which acetaminophen was the dominant substituent were synthesized where the asymmetric analogues bore an alkyne-terminated substituent. These complexes were applied as sensors towards the electro-oxidation of nitrite. In addition to comparing the asymmetric Pcs to the symmetric counterparts, an assessment on the different central metals as well as the method of electrode modification was made. From the studies performed, the results showed that the manganese complexes are generally better suited (more so when clicked on to the electrode) in the electrocatalysis of nitrite with a limit of detection and a catalytic rate values of 2.15 μM and 6.91 × 106 s−1 M−1 being recorded for the asymmetric MnPc.
- Full Text:
- Date Issued: 2021
- Authors: Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231425 , vital:49886 , xlink:href="https://doi.org/10.1149/1945-7111/ac377f"
- Description: The more conventional route to synthesizing asymmetric push-pull phthalocyanines (Pcs) involves pairing electron-donating substituents with electron-withdrawing groups in either an A3B or AB3 manner. In this work, a push-pull system fashioned from a substituent bearing different functional groups was created. Symmetric and asymmetric cobalt and manganese Pcs in which acetaminophen was the dominant substituent were synthesized where the asymmetric analogues bore an alkyne-terminated substituent. These complexes were applied as sensors towards the electro-oxidation of nitrite. In addition to comparing the asymmetric Pcs to the symmetric counterparts, an assessment on the different central metals as well as the method of electrode modification was made. From the studies performed, the results showed that the manganese complexes are generally better suited (more so when clicked on to the electrode) in the electrocatalysis of nitrite with a limit of detection and a catalytic rate values of 2.15 μM and 6.91 × 106 s−1 M−1 being recorded for the asymmetric MnPc.
- Full Text:
- Date Issued: 2021
Photocatalytic and solar radiation harvesting potential of a free-base porphyrin-zinc (II) phthalocyanine heterodyad functionalized polystyrene polymer membrane for the degradation of 4-chlorophenol
- Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185772 , vital:44422 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113142"
- Description: In this work a novel porphyrin-phthalocyanine heterodyad (complex 4) was synthesized and embedded in polystyrene polymer membranes. The singlet oxygen generation of 4 improved in comparison to the parent porphyrin and phthalocyanine complexes giving singlet oxygen quantum yields of 0.67 and 0.51 (in dimethyl sulfoxide) where the porphyrin and phthalocyanine complementarily absorb respectively. Successful Buchwald-Hartwig coupling of complex 4 to amine functionalized polystyrene ((NH2)PS) gave a complex loading of 24.6 mg complex/g 4-PS. Embedding of 4-PS in polystyrene polymer membrane yielded the photoactive 4-memb which proved to be capable of degrading 4-chlorophenol at reaction rates of at least 1.12 × 10−7 molL-1 min-1 and half-life of 193 min in a pseudo first order reaction at an initial concentration of 3.10 × 10-5. Also, light harvesting experiments proved 4-memb to be active in the whole 300–700 nm wavelength range with the greatest activity being under white light.
- Full Text:
- Date Issued: 2021
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185772 , vital:44422 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113142"
- Description: In this work a novel porphyrin-phthalocyanine heterodyad (complex 4) was synthesized and embedded in polystyrene polymer membranes. The singlet oxygen generation of 4 improved in comparison to the parent porphyrin and phthalocyanine complexes giving singlet oxygen quantum yields of 0.67 and 0.51 (in dimethyl sulfoxide) where the porphyrin and phthalocyanine complementarily absorb respectively. Successful Buchwald-Hartwig coupling of complex 4 to amine functionalized polystyrene ((NH2)PS) gave a complex loading of 24.6 mg complex/g 4-PS. Embedding of 4-PS in polystyrene polymer membrane yielded the photoactive 4-memb which proved to be capable of degrading 4-chlorophenol at reaction rates of at least 1.12 × 10−7 molL-1 min-1 and half-life of 193 min in a pseudo first order reaction at an initial concentration of 3.10 × 10-5. Also, light harvesting experiments proved 4-memb to be active in the whole 300–700 nm wavelength range with the greatest activity being under white light.
- Full Text:
- Date Issued: 2021
An octabrominated Sn (iv) tetraisopropylporphyrin as a photosensitizer dye for singlet oxygen biomedical applications
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186679 , vital:44524 , xlink:href="https://doi.org/10.1039/D0DT01915A"
- Description: Two novel Sn(IV) tetraisopropylphenylporphyrins have been synthesized to explore the effect of octabromination at the β-pyrrole positions on their photophysical properties and photodynamic activity. The lower energy Q band of an octabrominated complex lies at 675 nm well within the therapeutic window. The octabrominated dye has a relatively high singlet oxygen quantum yield of 0.78 in DMF and exhibits favorable photodynamic activity against MCF-7 cells with an IC50 value of 10.7 μM and a 5.74 log reduction value (5 μM) towards S. aureus under illumination at 660 nm for 60 min with a Thorlabs M660L3 LED (280 mW cm−2).
- Full Text:
- Date Issued: 2020
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186679 , vital:44524 , xlink:href="https://doi.org/10.1039/D0DT01915A"
- Description: Two novel Sn(IV) tetraisopropylphenylporphyrins have been synthesized to explore the effect of octabromination at the β-pyrrole positions on their photophysical properties and photodynamic activity. The lower energy Q band of an octabrominated complex lies at 675 nm well within the therapeutic window. The octabrominated dye has a relatively high singlet oxygen quantum yield of 0.78 in DMF and exhibits favorable photodynamic activity against MCF-7 cells with an IC50 value of 10.7 μM and a 5.74 log reduction value (5 μM) towards S. aureus under illumination at 660 nm for 60 min with a Thorlabs M660L3 LED (280 mW cm−2).
- Full Text:
- Date Issued: 2020
NIR Absorbing AzaBODIPY Dyes for pH Sensing
- Kubheka, Gugu, Mack, John, Nyokong, Tebello, Zhen, Shen
- Authors: Kubheka, Gugu , Mack, John , Nyokong, Tebello , Zhen, Shen
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186668 , vital:44523 , xlink:href="https://doi.org/10.3390/molecules25163689"
- Description: Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, in CH2Cl2. The effect of substituent position on the photophysical and pH sensing properties was analyzed through a comparison of the optical properties with the results of time-dependent density functional theory (TD-DFT) calculations. Protonation of the dimethylamino nitrogen atoms eliminates the intramolecular charge transfer properties of these compounds, and this results in a marked blue-shift of the main absorption bands to 696 and 730 nm, respectively, in CH2Cl2, and a fluorescence “turn-on” effect in the NIR region. The pH dependence studies reveal that the pKa values of the non-protonated 2a and 2b molecules are ca. 6.9 (±0.05) and 7.3 (±0.05), respectively, while that of the monoprotonated species for both dyes is ca. 1.4 (±0.05) making them potentially suitable for use as colorimetric pH indicators under highly acidic conditions.
- Full Text:
- Date Issued: 2020
- Authors: Kubheka, Gugu , Mack, John , Nyokong, Tebello , Zhen, Shen
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186668 , vital:44523 , xlink:href="https://doi.org/10.3390/molecules25163689"
- Description: Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, in CH2Cl2. The effect of substituent position on the photophysical and pH sensing properties was analyzed through a comparison of the optical properties with the results of time-dependent density functional theory (TD-DFT) calculations. Protonation of the dimethylamino nitrogen atoms eliminates the intramolecular charge transfer properties of these compounds, and this results in a marked blue-shift of the main absorption bands to 696 and 730 nm, respectively, in CH2Cl2, and a fluorescence “turn-on” effect in the NIR region. The pH dependence studies reveal that the pKa values of the non-protonated 2a and 2b molecules are ca. 6.9 (±0.05) and 7.3 (±0.05), respectively, while that of the monoprotonated species for both dyes is ca. 1.4 (±0.05) making them potentially suitable for use as colorimetric pH indicators under highly acidic conditions.
- Full Text:
- Date Issued: 2020
Corrosion resistance of aluminum against acid activation: Impact of benzothiazole-substituted gallium phthalocyanine
- Nnaji, Nnaemeka, Nwaji, Njemuwa N, Mack, John, Nyokong, Tebello
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa N , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187545 , vital:44670 , xlink:href="https://doi.org/10.3390/molecules24010207"
- Description: This study describes the adsorption behavior of organic inhibitors at the aluminum-HCl solution interface and their corrosion inhibition performance. The organic inhibitors employed are: 4-(benzo [d]thiazol-2ylthio)phthalonitrile (BTThio) and tetrakis[(benzo[d]thiazol-2-yl-thio)phthalocyaninato]gallium(III) chloride (ClGaBTThioPc). The corrosion behavior of these inhibitors is investigated using electrochemical and computational techniques. Open circuit potential results reveal predominant cathodic character for the mechanism of aluminum corrosion inhibition by the inhibitors. Inhibition efficiency values from potentiodynamic polarization measurements increase from 46.9 to 70.8% for BTThio and 59.7 to 81.0% for ClGaBTThioPc within the concentration range of 2 to 10 µM. Scanning electron microscopy (SEM) measurements reveal protection of the metal surface from acid attack, in the presence of the inhibitors and energy dispersive X-ray (EDX) measurements show that the most probable way by which the inhibitors protect the metal surface would be by shielding it from the corrosion attacks of Cl− from the acid. Quantum chemical parameters corroborate well with experimental findings.
- Full Text:
- Date Issued: 2019
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa N , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187545 , vital:44670 , xlink:href="https://doi.org/10.3390/molecules24010207"
- Description: This study describes the adsorption behavior of organic inhibitors at the aluminum-HCl solution interface and their corrosion inhibition performance. The organic inhibitors employed are: 4-(benzo [d]thiazol-2ylthio)phthalonitrile (BTThio) and tetrakis[(benzo[d]thiazol-2-yl-thio)phthalocyaninato]gallium(III) chloride (ClGaBTThioPc). The corrosion behavior of these inhibitors is investigated using electrochemical and computational techniques. Open circuit potential results reveal predominant cathodic character for the mechanism of aluminum corrosion inhibition by the inhibitors. Inhibition efficiency values from potentiodynamic polarization measurements increase from 46.9 to 70.8% for BTThio and 59.7 to 81.0% for ClGaBTThioPc within the concentration range of 2 to 10 µM. Scanning electron microscopy (SEM) measurements reveal protection of the metal surface from acid attack, in the presence of the inhibitors and energy dispersive X-ray (EDX) measurements show that the most probable way by which the inhibitors protect the metal surface would be by shielding it from the corrosion attacks of Cl− from the acid. Quantum chemical parameters corroborate well with experimental findings.
- Full Text:
- Date Issued: 2019
Inhibition of aluminium corrosion using benzothiazole and its phthalocyanine derivative
- Nnaji, Nnaemeka, Nwaji, Njemuwa, Fomo, Gertrude, Mack, John, Nyokong, Tebello
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa , Fomo, Gertrude , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186949 , vital:44550 , xlink:href="https://doi.org/10.1007/s12678-019-00538-1"
- Description: Cyclic voltammetry and potentiodynamic polarization techniques were used to study the effects of 4-[4-(1,3-benzothiazol2yl)phenoxy] phthalonitrile (BT) and tetrakis[(benzo[d]thiazol-2ylphenoxy) phthalocyaninato] gallium(III)chloride (ClGaBTPc) as aluminium corrosion inhibitors in 1.0 M hydrochloric acid. The presence of the inhibitors in the concentration range of 2 to 10 μM was found to retard the aluminium corrosion process such that the inhibition efficiency was found to range from 28.2 to 76.1% for BT and from 71.5 to 82.7% for ClGaBTPc. The latter was a better inhibitor. Scanning electron microscopy and energy-dispersive X-ray measurements reveal effective metal surface protection by the inhibitors, most probably by shielding it from the corrosion attacks of Cl− from the acid. The calculated quantum chemical parameters agreed with experimental results.
- Full Text:
- Date Issued: 2019
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa , Fomo, Gertrude , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186949 , vital:44550 , xlink:href="https://doi.org/10.1007/s12678-019-00538-1"
- Description: Cyclic voltammetry and potentiodynamic polarization techniques were used to study the effects of 4-[4-(1,3-benzothiazol2yl)phenoxy] phthalonitrile (BT) and tetrakis[(benzo[d]thiazol-2ylphenoxy) phthalocyaninato] gallium(III)chloride (ClGaBTPc) as aluminium corrosion inhibitors in 1.0 M hydrochloric acid. The presence of the inhibitors in the concentration range of 2 to 10 μM was found to retard the aluminium corrosion process such that the inhibition efficiency was found to range from 28.2 to 76.1% for BT and from 71.5 to 82.7% for ClGaBTPc. The latter was a better inhibitor. Scanning electron microscopy and energy-dispersive X-ray measurements reveal effective metal surface protection by the inhibitors, most probably by shielding it from the corrosion attacks of Cl− from the acid. The calculated quantum chemical parameters agreed with experimental results.
- Full Text:
- Date Issued: 2019
Nonlinear optical behavior of n-tuple decker phthalocyanines at the nanosecond regime
- Sekhosana, Kutloano E, Nyokong, Tebello
- Authors: Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234603 , vital:50212 , xlink:href="https://doi.org/10.1039/C9RA01836K"
- Description: The coordination system of rare-earth n-tuple decker phthalocyanines would be better suited with appropriate metal ions with the correct coordination number and the solvent system of the reaction, amongst other reasons, for the formation of n-tuple decker phthalocyanines. As a result, these complexes are very rare. In this manuscript, we present new n-tuple decker phthalocyanines in the form of double- (complex 2), quadruple- (complex 3a) and sextuple-decker phthalocyanines (complex 3b), all of which contain neodymium and cadmium metal ions. The primary focus is the investigation of the nonlinear optical (NLO) mechanisms responsible for the observed reverse saturable absorption. While the extension of the π-electron system has been found to enhance the nonlinear optical behavior of complexes 3a and 3b, a change in the NLO mechanisms has been observed, with complex 2 lacking the triplet state population, as revealed by a laser flash photolysis technique. It has also been established that the excited state absorption cross sections follow a clear order of magnitude for the complexes under investigation: σ23 (for 3b) > σ23 (for 3a) > σ1m (for 2). This trend evidences the effects of the extension of the π-electron system.
- Full Text:
- Date Issued: 2019
- Authors: Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234603 , vital:50212 , xlink:href="https://doi.org/10.1039/C9RA01836K"
- Description: The coordination system of rare-earth n-tuple decker phthalocyanines would be better suited with appropriate metal ions with the correct coordination number and the solvent system of the reaction, amongst other reasons, for the formation of n-tuple decker phthalocyanines. As a result, these complexes are very rare. In this manuscript, we present new n-tuple decker phthalocyanines in the form of double- (complex 2), quadruple- (complex 3a) and sextuple-decker phthalocyanines (complex 3b), all of which contain neodymium and cadmium metal ions. The primary focus is the investigation of the nonlinear optical (NLO) mechanisms responsible for the observed reverse saturable absorption. While the extension of the π-electron system has been found to enhance the nonlinear optical behavior of complexes 3a and 3b, a change in the NLO mechanisms has been observed, with complex 2 lacking the triplet state population, as revealed by a laser flash photolysis technique. It has also been established that the excited state absorption cross sections follow a clear order of magnitude for the complexes under investigation: σ23 (for 3b) > σ23 (for 3a) > σ1m (for 2). This trend evidences the effects of the extension of the π-electron system.
- Full Text:
- Date Issued: 2019
Preparation of NIR absorbing axial substituted tin (iv) porphyrins and their photocytotoxic properties
- Babu, Balaji, Amuhaya, Edith K, Oluwole, David O, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
- Full Text:
- Date Issued: 2019
- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
- Full Text:
- Date Issued: 2019
Wood preservation with gold hydroxyapatite system
- 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
- 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
- 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
Aza boron-pyridyl-isoindoline analogues
- Zhang, Hui, Wu, Yanping, Fan, Minhui, Xiao, Xuqiong, Mack, John, Kubheka, Gugu, Nyokong, Tebello, Lu, Hua
- Authors: Zhang, Hui , Wu, Yanping , Fan, Minhui , Xiao, Xuqiong , Mack, John , Kubheka, Gugu , Nyokong, Tebello , Lu, Hua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232912 , vital:50037 , xlink:href="https://doi.org/10.1039/C7NJ00707H"
- Description: Several aza boron-pyridyl-isoindoline analogues are synthesized through a facile and scale-up two step reaction using 1,2-naphthalenedicarbonitrile as a starting material. These analogues show broad envelopes of intense vibrational bands in the absorption spectra with moderate fluorescence quantum yields in solution and the solid-state. An analysis of the structure–property relationships is described based on X-ray crystallography, optical spectroscopy, and theoretical calculations.
- Full Text:
- Date Issued: 2017
- Authors: Zhang, Hui , Wu, Yanping , Fan, Minhui , Xiao, Xuqiong , Mack, John , Kubheka, Gugu , Nyokong, Tebello , Lu, Hua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232912 , vital:50037 , xlink:href="https://doi.org/10.1039/C7NJ00707H"
- Description: Several aza boron-pyridyl-isoindoline analogues are synthesized through a facile and scale-up two step reaction using 1,2-naphthalenedicarbonitrile as a starting material. These analogues show broad envelopes of intense vibrational bands in the absorption spectra with moderate fluorescence quantum yields in solution and the solid-state. An analysis of the structure–property relationships is described based on X-ray crystallography, optical spectroscopy, and theoretical calculations.
- Full Text:
- Date Issued: 2017
Nonlinear interactions of zinc phthalocyanine-graphene quantum dots nanocomposites: Investigation of effects of surface functionalization with heteroatoms
- Bankole, Owolabi M, Achadu, Ojodomo J, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Achadu, Ojodomo J , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188474 , vital:44757 , xlink:href="https://doi.org/10.1007/s10895-016-2008-8"
- Description: This study reports the development of functional optical limiting materials composed of pristine graphene (GQDs), nitrogen-doped (NGQDs) and sulfur-nitrogen co-doped (SNGQDs) graphene quantum dots covalently linked to mono-amino substituted zinc phthalocyanine (Pc). Open aperture Z-scan technique was employed to monitor the behaviour of the conjugates under tightly focussed Gaussian laser beam using a mode-locked Nd:YAG laser delivering 10 nanosecond (FWHM) pulses at 532 nm wavelength. Nonlinear effect due to reverse saturable absorption was the predominant mechanism; and was attributed to the moderately enhanced triplet population. The major factor(s) responsible for the enhanced nonlinearities in the Pc-NGQDs and Pc-SNGQDs was fully described and attributed to the surface defects caused by the presence of heteroatoms of N and S.
- Full Text:
- Date Issued: 2017
- Authors: Bankole, Owolabi M , Achadu, Ojodomo J , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188474 , vital:44757 , xlink:href="https://doi.org/10.1007/s10895-016-2008-8"
- Description: This study reports the development of functional optical limiting materials composed of pristine graphene (GQDs), nitrogen-doped (NGQDs) and sulfur-nitrogen co-doped (SNGQDs) graphene quantum dots covalently linked to mono-amino substituted zinc phthalocyanine (Pc). Open aperture Z-scan technique was employed to monitor the behaviour of the conjugates under tightly focussed Gaussian laser beam using a mode-locked Nd:YAG laser delivering 10 nanosecond (FWHM) pulses at 532 nm wavelength. Nonlinear effect due to reverse saturable absorption was the predominant mechanism; and was attributed to the moderately enhanced triplet population. The major factor(s) responsible for the enhanced nonlinearities in the Pc-NGQDs and Pc-SNGQDs was fully described and attributed to the surface defects caused by the presence of heteroatoms of N and S.
- Full Text:
- Date Issued: 2017
Comparative studies on photophysical and optical limiting characterizations of low symmetry phthalocyanine linked to Fe 3 O 4–Ag core–shell or hybrid nanoparticles
- Bankole, Owolabi M, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188788 , vital:44785 , xlink:href="https://doi.org/10.1039/C6NJ01511E"
- Description: Photophysical and nonlinear optical (NLO) behaviours of low symmetry zinc phthalocyanine (1) linked to Fe3O4/Ag core–shell (represented as Fe/Ag) or Fe3O4–Ag hybrid (represented as FeAg) nanoparticles were investigated in DMSO. Triplet quantum yields and NLO parameters of phthalocyanine improved due to the combined effects of magnetic–metallic nanoparticles. A direct relationship between the increased triplet excited state absorptions by already excited molecules and reverse saturable absorption (RSA) was established as the predominant mechanism responsible for nonlinearity of the samples. Our findings show that, at the same approximate concentrations and conditions, 1-FeAg enhanced the OL potentials of 1 more than 1-Fe/Ag.
- Full Text:
- Date Issued: 2016
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188788 , vital:44785 , xlink:href="https://doi.org/10.1039/C6NJ01511E"
- Description: Photophysical and nonlinear optical (NLO) behaviours of low symmetry zinc phthalocyanine (1) linked to Fe3O4/Ag core–shell (represented as Fe/Ag) or Fe3O4–Ag hybrid (represented as FeAg) nanoparticles were investigated in DMSO. Triplet quantum yields and NLO parameters of phthalocyanine improved due to the combined effects of magnetic–metallic nanoparticles. A direct relationship between the increased triplet excited state absorptions by already excited molecules and reverse saturable absorption (RSA) was established as the predominant mechanism responsible for nonlinearity of the samples. Our findings show that, at the same approximate concentrations and conditions, 1-FeAg enhanced the OL potentials of 1 more than 1-Fe/Ag.
- Full Text:
- Date Issued: 2016
Effects of pluronic silica nanoparticles on the photophysical and photodynamic therapy behavior of triphenyl-p-phenoxy benzoic acid metalloporphyrins
- Managa, Muthumuni, Britton, Jonathan, Prinsloo, Earl, Nyokong, Tebello
- Authors: Managa, Muthumuni , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239698 , vital:50756 , xlink:href="https://doi.org/10.1080/00958972.2016.1236372"
- Description: 5, 10, 15, Triphenyl-20-p-phenoxy benzoic acid porphyrins (P) containing Zn (ZnP), Ga (GaP), and Si (SiP) were synthesized and conjugated to pluronic-silica (PluS) nanoparticles (NPs) where the fluorescence and singlet oxygen generating behavior of the porphyrins were investigated. The highest singlet oxygen quantum yield (ΦΔ) was obtained for ZnP. When the porphyrins were conjugated to the PluS NPs, the ΦΔ was quenched and fluorescence was enhanced. The pore size of the NPs upon conjugation decreased from 18.9 nm for PluS NPs to 2.4 nm (for ZnP as an example) as determined by applying the Brunauer–Emmett–Teller method. The porphyrin complexes and their conjugates were tested for their photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. It was found that ZnP and its conjugate showed the highest PDT activity. The p > 0.05 indicated that ZnP is significantly different than GaP and SiP.
- Full Text:
- Date Issued: 2016
- Authors: Managa, Muthumuni , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239698 , vital:50756 , xlink:href="https://doi.org/10.1080/00958972.2016.1236372"
- Description: 5, 10, 15, Triphenyl-20-p-phenoxy benzoic acid porphyrins (P) containing Zn (ZnP), Ga (GaP), and Si (SiP) were synthesized and conjugated to pluronic-silica (PluS) nanoparticles (NPs) where the fluorescence and singlet oxygen generating behavior of the porphyrins were investigated. The highest singlet oxygen quantum yield (ΦΔ) was obtained for ZnP. When the porphyrins were conjugated to the PluS NPs, the ΦΔ was quenched and fluorescence was enhanced. The pore size of the NPs upon conjugation decreased from 18.9 nm for PluS NPs to 2.4 nm (for ZnP as an example) as determined by applying the Brunauer–Emmett–Teller method. The porphyrin complexes and their conjugates were tested for their photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. It was found that ZnP and its conjugate showed the highest PDT activity. The p > 0.05 indicated that ZnP is significantly different than GaP and SiP.
- Full Text:
- Date Issued: 2016
Fluorescence properties of alloyed ZnSeS quantum dots overcoated with ZnTe and ZnTe/ZnS shells
- Adegoke, Oluwasesan, Mashazi, Philani N, Nyokong, Tebello, Forbes, Patricia B C
- Authors: Adegoke, Oluwasesan , Mashazi, Philani N , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240754 , vital:50868 , xlink:href="https://doi.org/10.1016/j.optmat.2016.02.024"
- Description: Fluorescent alloyed ternary ZnSeS quantum dots (QDs) have been synthesized via the pyrolysis of organometallic precursors. The effects of passivation of ZnTe and ZnTe/ZnS shells on the optical properties of the ternary alloyed ZnSeS core have been studied. A ligand exchange reaction using L-cysteine as a capping ligand was used to obtain water-soluble nanocrystals. The nanocrystals were each characterized by UV/vis absorption and fluorescence spectroscopy, transmission electron microscopy, X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) quantum yield (QY) of alloyed ZnSeS QDs was 14% and this value increased to 27% when ZnTe was overcoated around the surface but further coating with a ZnS shell decreased the PL QY slightly to 24%. This implies that ZnTe shell suppressed non-radiative recombination exciton states in the alloyed core while further layering with a ZnS shell offered no further improvement in suppressing the defect states. XPS analysis confirmed the presence of the first shell layering but showed a weakened intensity signal of S (2p) and Se (3d) for the ZnSeS/ZnTe/ZnS QDs. Our work demonstrates for the first time that shell passivation of alloyed Zn-based QDs can offer improved optical properties. We hope the optical information presented in this work will be useful in the selection of alloyed Zn-based QDs appropriate for the intended application.
- Full Text:
- Date Issued: 2016
- Authors: Adegoke, Oluwasesan , Mashazi, Philani N , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240754 , vital:50868 , xlink:href="https://doi.org/10.1016/j.optmat.2016.02.024"
- Description: Fluorescent alloyed ternary ZnSeS quantum dots (QDs) have been synthesized via the pyrolysis of organometallic precursors. The effects of passivation of ZnTe and ZnTe/ZnS shells on the optical properties of the ternary alloyed ZnSeS core have been studied. A ligand exchange reaction using L-cysteine as a capping ligand was used to obtain water-soluble nanocrystals. The nanocrystals were each characterized by UV/vis absorption and fluorescence spectroscopy, transmission electron microscopy, X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) quantum yield (QY) of alloyed ZnSeS QDs was 14% and this value increased to 27% when ZnTe was overcoated around the surface but further coating with a ZnS shell decreased the PL QY slightly to 24%. This implies that ZnTe shell suppressed non-radiative recombination exciton states in the alloyed core while further layering with a ZnS shell offered no further improvement in suppressing the defect states. XPS analysis confirmed the presence of the first shell layering but showed a weakened intensity signal of S (2p) and Se (3d) for the ZnSeS/ZnTe/ZnS QDs. Our work demonstrates for the first time that shell passivation of alloyed Zn-based QDs can offer improved optical properties. We hope the optical information presented in this work will be useful in the selection of alloyed Zn-based QDs appropriate for the intended application.
- Full Text:
- Date Issued: 2016
Lipophilic M(α,α′-OC5H11)8phthalocyanines (M = H2 and Ni(II)): synthesis, electronic structure, and their utility for highly efficient carbonyl reductions
- Jiang, Yu, Li, Minzhi, Liang, Xu, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Qin, Mingfeng, Zhu, Weihua
- Authors: Jiang, Yu , Li, Minzhi , Liang, Xu , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Qin, Mingfeng , Zhu, Weihua
- Date: 2015-10-07
- Subjects: Dalton Transactions (2015), 44, 18237-18246, doi:10.1039/c5dt03256c
- Language: English
- Type: Article
- Identifier: vital:7282 , http://hdl.handle.net/10962/d1020322
- Description: A lipophilic and electron-rich phthalocyanine (α,α′-n-OC5H11)8-H2Pc and its nickel(II) complex (α,α′-n-OC5H11)8-Ni(II)Pc have been synthesized and characterized. Detailed analyses of the electronic structure were carried out by spectroscopy, electrochemistry, spectroelectrochemistry, and TD-DFT calculations. A series of experiments demonstrate that the (α,α′-n-OC5H11)8-Ni(II)Pc complex can be used as a catalyst for highly efficient carbonyl reductions. , Original publication is available at http://dx.doi.org/10.1039/C5DT03256C
- Full Text:
- Authors: Jiang, Yu , Li, Minzhi , Liang, Xu , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Qin, Mingfeng , Zhu, Weihua
- Date: 2015-10-07
- Subjects: Dalton Transactions (2015), 44, 18237-18246, doi:10.1039/c5dt03256c
- Language: English
- Type: Article
- Identifier: vital:7282 , http://hdl.handle.net/10962/d1020322
- Description: A lipophilic and electron-rich phthalocyanine (α,α′-n-OC5H11)8-H2Pc and its nickel(II) complex (α,α′-n-OC5H11)8-Ni(II)Pc have been synthesized and characterized. Detailed analyses of the electronic structure were carried out by spectroscopy, electrochemistry, spectroelectrochemistry, and TD-DFT calculations. A series of experiments demonstrate that the (α,α′-n-OC5H11)8-Ni(II)Pc complex can be used as a catalyst for highly efficient carbonyl reductions. , Original publication is available at http://dx.doi.org/10.1039/C5DT03256C
- Full Text:
Fluorescence Behaviour of an Aluminium Octacarboxy Phthalocyanine-NaYGdF 4
- Taylor, Jessica, Litwinski, Christian, Nyokong, Tebello, Antunes, Edith M
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189503 , vital:44852 , xlink:href="https://doi.org/10.1007/s10895-015-1539-8"
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions).
- Full Text:
- Date Issued: 2015
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189503 , vital:44852 , xlink:href="https://doi.org/10.1007/s10895-015-1539-8"
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions).
- Full Text:
- Date Issued: 2015