4-Azidoaniline-based electropolymer as a building block for functionalisation of conductive surfaces
- Coates, Megan, Elamari, Hichem, Girard, Christian, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Coates, Megan , Elamari, Hichem , Girard, Christian , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244404 , vital:51254 , xlink:href="https://doi.org/10.1016/j.jelechem.2012.01.001"
- Description: We propose in this work to compare three approaches using 4-azidoaniline combined with “click” chemistry and electrochemistry to anchor ferrocene moieties at glassy carbon surfaces. The immobilisation of a newly synthesised molecule, 4-(4-ferrocenyl-1H-1,2,3-triazol-1-yl)aniline, through direct electropolymerisation or via in situ diazotization followed by electrografting is studied by analysing the samples by XPS and electrochemistry.
- Full Text:
- Date Issued: 2012
4-Azidoaniline-based electropolymer as a building block for functionalisation of conductive surfaces
- Authors: Coates, Megan , Elamari, Hichem , Girard, Christian , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244404 , vital:51254 , xlink:href="https://doi.org/10.1016/j.jelechem.2012.01.001"
- Description: We propose in this work to compare three approaches using 4-azidoaniline combined with “click” chemistry and electrochemistry to anchor ferrocene moieties at glassy carbon surfaces. The immobilisation of a newly synthesised molecule, 4-(4-ferrocenyl-1H-1,2,3-triazol-1-yl)aniline, through direct electropolymerisation or via in situ diazotization followed by electrografting is studied by analysing the samples by XPS and electrochemistry.
- Full Text:
- Date Issued: 2012
A comparative study on the sensitive detection of hydroxyl radical using thiol-capped CdTe and CdTe/ZnS quantum dots
- Adegoke, Oluwasesan, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242778 , vital:51077 , xlink:href="https://doi.org/10.1007/s10895-012-1089-2"
- Description: Four types of water-soluble luminescent quantum dots (QDs) whose surface was functionlaized with thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), or glutathione (GSH), were investigated for the sensitive and selective detection of hydroxyl radical (●OH) in aqueous media. It was found that the type of capping agent and QD influenced the sensitivity of the probe. The order of sensitivity of the probe was: GSH-CdTe@ZnS > MPA-CdTe@ZnS > TGA-CdTe > MPA-CdTe QDs. Under the optimum conditions, a limit of detection as low as 8.5 × 10-8 M was obtained using GSH-CdTe@ZnS. The effects of foreign reactive oxygen species and the Fenton reactants and products as possible interferences on the proposed probe were negligible for CdTe@ZnS QDs. Besides, experimental results indicated that CdTe@ZnS QDs were more attractive for the selective recognition of ●OH than CdTe QDs. The mechanistic reaction pathway between the QDs and ●OH is proposed.
- Full Text:
- Date Issued: 2012
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242778 , vital:51077 , xlink:href="https://doi.org/10.1007/s10895-012-1089-2"
- Description: Four types of water-soluble luminescent quantum dots (QDs) whose surface was functionlaized with thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), or glutathione (GSH), were investigated for the sensitive and selective detection of hydroxyl radical (●OH) in aqueous media. It was found that the type of capping agent and QD influenced the sensitivity of the probe. The order of sensitivity of the probe was: GSH-CdTe@ZnS > MPA-CdTe@ZnS > TGA-CdTe > MPA-CdTe QDs. Under the optimum conditions, a limit of detection as low as 8.5 × 10-8 M was obtained using GSH-CdTe@ZnS. The effects of foreign reactive oxygen species and the Fenton reactants and products as possible interferences on the proposed probe were negligible for CdTe@ZnS QDs. Besides, experimental results indicated that CdTe@ZnS QDs were more attractive for the selective recognition of ●OH than CdTe QDs. The mechanistic reaction pathway between the QDs and ●OH is proposed.
- Full Text:
- Date Issued: 2012
A highly selective and sensitive pyridylazo-2-naphthol-poly (acrylic acid) functionalized electrospun nanofiber fluorescence “turn-off” chemosensory system for Ni 2+
- Adewuyi, Sheriff, Ondigo, Dezzline A, Zugle, Ruphino, Tshentu, Zenixole R, Nyokong, Tebello, Torto, Nelson
- Authors: Adewuyi, Sheriff , Ondigo, Dezzline A , Zugle, Ruphino , Tshentu, Zenixole R , Nyokong, Tebello , Torto, Nelson
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246012 , vital:51428 , xlink:href="https://doi.org/10.1039/C2AY25182E"
- Description: A fluorescent nanofiber probe for the determination of Ni2+ was developed via the electrospinning of a covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymer. Fluorescent nanofibers with diameters in the range 230–800 nm were produced with uniformly dispersed fluorophores. The excitation and emission fluorescence were at wavelengths 479 and 557 nm respectively, thereby exhibiting a good Stokes' shift. This Ni2+ probe that employs fluorescence quenching in a solid receptor–fluorophore system exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 μg mL−1 based on the Stern–Volmer mechanism. The probe achieved a detection limit (3δ/S) of 0.07 ng mL−1 and a precision, calculated as a relative standard deviation (RSD) of more than 4% (n = 8). The concentration of Ni2+ in a certified reference material (SEP-3) was found to be 0.8986 μg mL−1, which is significantly comparable with the certified value of 0.8980 μg mL−1. The accuracy of the determinations, expressed as a relative error between the certified and the observed values of certified reference groundwater was ≤0.1%. The versatility of the nanofiber probe was demonstrated by affording simple, rapid and selective detection of Ni2+ in the presence of other competing metal ions by direct analysis, without employing any further sample handling steps.
- Full Text:
- Date Issued: 2012
- Authors: Adewuyi, Sheriff , Ondigo, Dezzline A , Zugle, Ruphino , Tshentu, Zenixole R , Nyokong, Tebello , Torto, Nelson
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246012 , vital:51428 , xlink:href="https://doi.org/10.1039/C2AY25182E"
- Description: A fluorescent nanofiber probe for the determination of Ni2+ was developed via the electrospinning of a covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymer. Fluorescent nanofibers with diameters in the range 230–800 nm were produced with uniformly dispersed fluorophores. The excitation and emission fluorescence were at wavelengths 479 and 557 nm respectively, thereby exhibiting a good Stokes' shift. This Ni2+ probe that employs fluorescence quenching in a solid receptor–fluorophore system exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 μg mL−1 based on the Stern–Volmer mechanism. The probe achieved a detection limit (3δ/S) of 0.07 ng mL−1 and a precision, calculated as a relative standard deviation (RSD) of more than 4% (n = 8). The concentration of Ni2+ in a certified reference material (SEP-3) was found to be 0.8986 μg mL−1, which is significantly comparable with the certified value of 0.8980 μg mL−1. The accuracy of the determinations, expressed as a relative error between the certified and the observed values of certified reference groundwater was ≤0.1%. The versatility of the nanofiber probe was demonstrated by affording simple, rapid and selective detection of Ni2+ in the presence of other competing metal ions by direct analysis, without employing any further sample handling steps.
- Full Text:
- Date Issued: 2012
A study on the morphology of thin copper films on para-aramid yarns and their influence on the yarn’s electro-conductive and mechanical properties
- Schwarz, Anne, Hakuzimana, Jean, Westbroek, Philippe, Mey, Gilbert De, Priniotakis, Georgios, Nyokong, Tebello, Langenhove, Lieva Van
- Authors: Schwarz, Anne , Hakuzimana, Jean , Westbroek, Philippe , Mey, Gilbert De , Priniotakis, Georgios , Nyokong, Tebello , Langenhove, Lieva Van
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243487 , vital:51157 , xlink:href="https://doi.org/10.1177/0040517511431291"
- Description: The latest technological advances in new materials and devices enabled wearable systems to be created by utilizing textile solutions. These solutions require electro-conductive yarns as a basic component. Although the production of electroconductive yarn is widely reported, research is still necessary to characterize them to advance their electro-conductive and mechanical properties. Hence, we served this need and characterized copper-coated para-aramid yarns produced by an in-house developed electroless deposition method. In this paper we present our investigation on the yarn’s copper layer characteristics after deposition. Furthermore, we looked, in depth, at the yarn’s electro-conductive properties before and after washing as well as their mechanical properties before and after copper deposition. We found a dependency of the copper layer morphology on its deposition time. This is directly correlated to the resulting layer thickness and hence to the yarn’s electro-conductive properties, demonstrating the autocatalytic nature of the coating process. Above that, the electro-conductive properties of the coated yarn linearly decrease with washing cycles. Furthermore, the copper coating impairs the yarn’s mechanical properties decreasing its specific stress at break by 30%.
- Full Text:
- Date Issued: 2012
- Authors: Schwarz, Anne , Hakuzimana, Jean , Westbroek, Philippe , Mey, Gilbert De , Priniotakis, Georgios , Nyokong, Tebello , Langenhove, Lieva Van
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243487 , vital:51157 , xlink:href="https://doi.org/10.1177/0040517511431291"
- Description: The latest technological advances in new materials and devices enabled wearable systems to be created by utilizing textile solutions. These solutions require electro-conductive yarns as a basic component. Although the production of electroconductive yarn is widely reported, research is still necessary to characterize them to advance their electro-conductive and mechanical properties. Hence, we served this need and characterized copper-coated para-aramid yarns produced by an in-house developed electroless deposition method. In this paper we present our investigation on the yarn’s copper layer characteristics after deposition. Furthermore, we looked, in depth, at the yarn’s electro-conductive properties before and after washing as well as their mechanical properties before and after copper deposition. We found a dependency of the copper layer morphology on its deposition time. This is directly correlated to the resulting layer thickness and hence to the yarn’s electro-conductive properties, demonstrating the autocatalytic nature of the coating process. Above that, the electro-conductive properties of the coated yarn linearly decrease with washing cycles. Furthermore, the copper coating impairs the yarn’s mechanical properties decreasing its specific stress at break by 30%.
- Full Text:
- Date Issued: 2012
CdTe quantum dots functionalized with 4-amino-2, 2, 6, 6-tetramethylpiperidine-N-oxide as luminescent nanoprobe for the sensitive recognition of bromide ion
- Adegoke, Oluwasesan, Hosten, Eric C, McCleland, Cedric, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244393 , vital:51253 , xlink:href="https://doi.org/10.1016/j.aca.2012.01.040"
- Description: A novel bromide ion-selective modified nanoprobe sensor based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT)-functionalized CdTe quantum dots (QDs-4AT) has been developed. Fluorescence quenching of the QDs by 4AT was observed. The functionalized QDs-4AT nanoprobe allowed a highly sensitive determination of bromide ion via analyte-induced change in the photoluminescence (fluorescence recovery) of the modified QDs. A detection limit of 0.6 nM of bromide ion was obtained, while the interfering effect of other inorganic cations and anions was investigated to examine the selectivity of the nanoprobe. The linear range was between 0.01 and 0.13 μM. Combined fluorescence lifetime and electron paramagnetic resonance measurements confirmed electron transfer processes between bromide ion and QDs-4AT.
- Full Text:
- Date Issued: 2012
- Authors: Adegoke, Oluwasesan , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244393 , vital:51253 , xlink:href="https://doi.org/10.1016/j.aca.2012.01.040"
- Description: A novel bromide ion-selective modified nanoprobe sensor based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT)-functionalized CdTe quantum dots (QDs-4AT) has been developed. Fluorescence quenching of the QDs by 4AT was observed. The functionalized QDs-4AT nanoprobe allowed a highly sensitive determination of bromide ion via analyte-induced change in the photoluminescence (fluorescence recovery) of the modified QDs. A detection limit of 0.6 nM of bromide ion was obtained, while the interfering effect of other inorganic cations and anions was investigated to examine the selectivity of the nanoprobe. The linear range was between 0.01 and 0.13 μM. Combined fluorescence lifetime and electron paramagnetic resonance measurements confirmed electron transfer processes between bromide ion and QDs-4AT.
- Full Text:
- Date Issued: 2012
Characterization of 2,(3)-tetra-(4-oxo-benzamide) phthalocyaninato cobalt (II)—single walled carbon nanotube conjugate platforms and their use in electrocatalysis of amitrole
- Mugadza, Tawanda, Arslanoğlu, Yasin, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244382 , vital:51252 , xlink:href="https://doi.org/10.1016/j.electacta.2012.02.041"
- Description: In this paper we report on the use of carboxylic acid functionalized single walled carbon nanotubes (SWCNT) in the synthesis of 2,(3)-tetra-(4-oxo-benzamide)phthalocyaninato cobalt (II)–single walled carbon nanotube conjugates (CoTOBPc–SWCNT), their characterization and application in the electrocatalytic oxidation of amitrole. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were used for the detection of amitrole on the modified glassy carbon electrode. The catalytic rate constant was 1.6 × 103 M−1 s−1 and the apparent electron rate transfer constant was 1.5 × 10−5 cm s−1. The linear dynamic range was 1.0 × 10−6–3.0 × 10−5 M, with a sensitivity of ∼1.13 A mol−1 L cm−2.
- Full Text:
- Date Issued: 2012
- Authors: Mugadza, Tawanda , Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244382 , vital:51252 , xlink:href="https://doi.org/10.1016/j.electacta.2012.02.041"
- Description: In this paper we report on the use of carboxylic acid functionalized single walled carbon nanotubes (SWCNT) in the synthesis of 2,(3)-tetra-(4-oxo-benzamide)phthalocyaninato cobalt (II)–single walled carbon nanotube conjugates (CoTOBPc–SWCNT), their characterization and application in the electrocatalytic oxidation of amitrole. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were used for the detection of amitrole on the modified glassy carbon electrode. The catalytic rate constant was 1.6 × 103 M−1 s−1 and the apparent electron rate transfer constant was 1.5 × 10−5 cm s−1. The linear dynamic range was 1.0 × 10−6–3.0 × 10−5 M, with a sensitivity of ∼1.13 A mol−1 L cm−2.
- Full Text:
- Date Issued: 2012
Comparison of carbon screen-printed and disk electrodes in the detection of antioxidants using CoPc derivatives
- Matemadombo, Fungisai, Apetrei, Constantin, Nyokong, Tebello, Rodríguez-Méndez, María Luz, de Saja, José Antonio
- Authors: Matemadombo, Fungisai , Apetrei, Constantin , Nyokong, Tebello , Rodríguez-Méndez, María Luz , de Saja, José Antonio
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244371 , vital:51251 , xlink:href="https://doi.org/10.1016/j.snb.2012.02.088"
- Description: Cobalt phthalocyanine (CoPc) and cobalt phthalocyanine carboxylic derivatives (CoTCPc and CoOCPc) have been used as electrocatalysts for the detection of the antioxidants vanillic acid, caffeic acid, pyrogallol, and ascorbic acid on screen-printed carbon and disk electrode surfaces. The cobalt phthalocyanines were used to detect vanillic acid (with limit of detection ranging from 1.15 μM to 2.42 μM at potentials of 0.55–0.88 V vs. Ag|AgCl), caffeic acid (with limit of detection ranging from 1.17 μM to 2.20 μM at potentials of 0.30–0.81 V vs. Ag|AgCl), pyrogallol (with limit of detection ranging from 1.16 μM to 3.63 μM at potentials of 0.52–0.63 V vs. Ag|AgCl), and ascorbic acid (with limit of detection ranging from 1.16 μM to 1.58 μM at potentials of 0.34–0.46 V vs. Ag|AgCl). The kinetic studies also demonstrate diffusion-controlled processes at the electrode surface. The SPCE electrodes have better detection properties towards vanillic acid, caffeic acid, pyrogallol while the disk electrodes had better ascorbic acid detection properties as proven by kinetic studies. Both types CoPc-influenced electrodes show 100% discrimination of the antioxidants.
- Full Text:
- Date Issued: 2012
- Authors: Matemadombo, Fungisai , Apetrei, Constantin , Nyokong, Tebello , Rodríguez-Méndez, María Luz , de Saja, José Antonio
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244371 , vital:51251 , xlink:href="https://doi.org/10.1016/j.snb.2012.02.088"
- Description: Cobalt phthalocyanine (CoPc) and cobalt phthalocyanine carboxylic derivatives (CoTCPc and CoOCPc) have been used as electrocatalysts for the detection of the antioxidants vanillic acid, caffeic acid, pyrogallol, and ascorbic acid on screen-printed carbon and disk electrode surfaces. The cobalt phthalocyanines were used to detect vanillic acid (with limit of detection ranging from 1.15 μM to 2.42 μM at potentials of 0.55–0.88 V vs. Ag|AgCl), caffeic acid (with limit of detection ranging from 1.17 μM to 2.20 μM at potentials of 0.30–0.81 V vs. Ag|AgCl), pyrogallol (with limit of detection ranging from 1.16 μM to 3.63 μM at potentials of 0.52–0.63 V vs. Ag|AgCl), and ascorbic acid (with limit of detection ranging from 1.16 μM to 1.58 μM at potentials of 0.34–0.46 V vs. Ag|AgCl). The kinetic studies also demonstrate diffusion-controlled processes at the electrode surface. The SPCE electrodes have better detection properties towards vanillic acid, caffeic acid, pyrogallol while the disk electrodes had better ascorbic acid detection properties as proven by kinetic studies. Both types CoPc-influenced electrodes show 100% discrimination of the antioxidants.
- Full Text:
- Date Issued: 2012
Electrocatalytic behavior of cobalt phthalocyanine complexes immobilized on glassy carbon electrode towards the reduction of dicrotophos pesticide
- Vilakazi, Sibulelo, Nyokong, Tebello, Fukuda, Takamitsu, Kobayashi, Nagao
- Authors: Vilakazi, Sibulelo , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245832 , vital:51409 , xlink:href="https://doi.org/10.1142/S1088424612501040"
- Description: Electrocatalytic properties of cobalt phthalocyanine (CoPc), cobalt tetra-carboxy phthalocyanine (CoTCPc) and cobalt octa-carboxy (CoOCPc), towards the detection of dicrotophos have been studied. Catalytic behavior towards the reduction of dicrotophos was found to be dependent on the pH, as well as the substitution on the phthalocyanine ring. Strong electron withdrawing groups on the phthalocyanine ring yielded best catalysis as evidenced by the enhancement of the reduction peak current, (~5 fold) compared to the bare glassy carbon electrode. The analysis gave a good detection limit of 1.25 × 10-7 M, and good linearity for the studied concentration range. A high Tafel slope value was obtained, indicating a strong interaction between dicrotophos and the cobalt phthalocyanine complex.
- Full Text:
- Date Issued: 2012
- Authors: Vilakazi, Sibulelo , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245832 , vital:51409 , xlink:href="https://doi.org/10.1142/S1088424612501040"
- Description: Electrocatalytic properties of cobalt phthalocyanine (CoPc), cobalt tetra-carboxy phthalocyanine (CoTCPc) and cobalt octa-carboxy (CoOCPc), towards the detection of dicrotophos have been studied. Catalytic behavior towards the reduction of dicrotophos was found to be dependent on the pH, as well as the substitution on the phthalocyanine ring. Strong electron withdrawing groups on the phthalocyanine ring yielded best catalysis as evidenced by the enhancement of the reduction peak current, (~5 fold) compared to the bare glassy carbon electrode. The analysis gave a good detection limit of 1.25 × 10-7 M, and good linearity for the studied concentration range. A high Tafel slope value was obtained, indicating a strong interaction between dicrotophos and the cobalt phthalocyanine complex.
- Full Text:
- Date Issued: 2012
Electrospun polyacrylic acid polymer fibers functionalized with metallophthalocyanines for photosensitizing and gas sensing applications
- Zugle, Ruphino, Nyokong, Tebello
- Authors: Zugle, Ruphino , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243543 , vital:51162 , xlink:href="https://doi.org/10.1080/10601325.2012.662006"
- Description: The photophysical and photochemical properties of tetraaminophthalocyanine complexes of lutetium and zinc covalently linked to polyacrylic acid were studied alongside those of unsubstituted zinc phthalocyanine within the same polymeric fiber matrix. All three phthalocyanines within the solid fiber matrices showed photoactivity by the generation of singlet oxygen as was observed in solution. The fluorescence behaviors of the composite fibers equally parallel those in solution. For the unsubstituted zinc phthalocyanine composite, the fiber showed fluorescence quenching on interaction with gaseous nitrogen dioxide similar to that in DMF and, thus could be a promising nanofabric material in developing optoelectronic devices that are responsive to the gas.
- Full Text:
- Date Issued: 2012
- Authors: Zugle, Ruphino , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243543 , vital:51162 , xlink:href="https://doi.org/10.1080/10601325.2012.662006"
- Description: The photophysical and photochemical properties of tetraaminophthalocyanine complexes of lutetium and zinc covalently linked to polyacrylic acid were studied alongside those of unsubstituted zinc phthalocyanine within the same polymeric fiber matrix. All three phthalocyanines within the solid fiber matrices showed photoactivity by the generation of singlet oxygen as was observed in solution. The fluorescence behaviors of the composite fibers equally parallel those in solution. For the unsubstituted zinc phthalocyanine composite, the fiber showed fluorescence quenching on interaction with gaseous nitrogen dioxide similar to that in DMF and, thus could be a promising nanofabric material in developing optoelectronic devices that are responsive to the gas.
- Full Text:
- Date Issued: 2012
Facile deposition of gold nanoparticle thin films on semi-permeable cellulose substrate
- Sosibo, Ndabenhle, Mdluli, Phumlani, Mashazi, Philani N, Tshikhudo, Robert, Skepu, Amanda, Vilakazi, Sibulelo, Nyokong, Tebello
- Authors: Sosibo, Ndabenhle , Mdluli, Phumlani , Mashazi, Philani N , Tshikhudo, Robert , Skepu, Amanda , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242638 , vital:51063 , xlink:href="https://doi.org/10.1016/j.matlet.2012.08.043"
- Description: This study reports the facile method for the deposition of gold nanoparticle thin film onto a monoporous semi-permeable cellulose membrane through the diffusion of borohydride ions leading to the reduction of AuCl4− ions. The synthesis of gold nanoparticle thin film was deposited on one side of the membrane that was exposed to AuCl4− ions while the other side containing a reducing agent remained clear. The gold nanoparticle thin film exhibited a broad surface plasmon resonance (SPR) peak at 529 nm. Various characterization techniques were employed and all demonstrated the presence of gold thin film. The reported method represents a simplistic method for the deposition of gold nanoparticle thin films and various other metal nanoparticles may be deposited following this method.
- Full Text:
- Date Issued: 2012
- Authors: Sosibo, Ndabenhle , Mdluli, Phumlani , Mashazi, Philani N , Tshikhudo, Robert , Skepu, Amanda , Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242638 , vital:51063 , xlink:href="https://doi.org/10.1016/j.matlet.2012.08.043"
- Description: This study reports the facile method for the deposition of gold nanoparticle thin film onto a monoporous semi-permeable cellulose membrane through the diffusion of borohydride ions leading to the reduction of AuCl4− ions. The synthesis of gold nanoparticle thin film was deposited on one side of the membrane that was exposed to AuCl4− ions while the other side containing a reducing agent remained clear. The gold nanoparticle thin film exhibited a broad surface plasmon resonance (SPR) peak at 529 nm. Various characterization techniques were employed and all demonstrated the presence of gold thin film. The reported method represents a simplistic method for the deposition of gold nanoparticle thin films and various other metal nanoparticles may be deposited following this method.
- Full Text:
- Date Issued: 2012
Imidazole-functionalized polymer microspheres and fibers–useful materials for immobilization of oxovanadium (IV) catalysts
- Walmsley, Ryan S, Ogunlaja, Adeniyi S, Coombes, Matthew J, Chidawanyika, Wadzanai J U, Litwinski, Christian, Torto, Nelson, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Walmsley, Ryan S , Ogunlaja, Adeniyi S , Coombes, Matthew J , Chidawanyika, Wadzanai J U , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246041 , vital:51431 , xlink:href="https://doi.org/10.1039/C2JM15485D"
- Description: Both polymer microspheres and microfibers containing the imidazole functionality have been prepared and used to immobilize oxovanadium(IV). The average diameters and BET surface areas of the microspheres were 322 μm and 155 m2 g−1 while the fibers were 1.85 μm and 52 m2 g−1, respectively. XPS and microanalysis confirmed the incorporation of imidazole and vanadium in the polymeric materials. The catalytic activity of both materials was evaluated using the hydrogen peroxide facilitated oxidation of thioanisole. The microspheres were applied in a typical laboratory batch reactor set-up and quantitative conversions (>99%) were obtained in under 240 min with turn-over frequencies ranging from 21.89 to 265.53 h−1, depending on the quantity of catalyst and temperature. The microspherical catalysts also proved to be recyclable with no drop in activity being observed after three successive reactions. The vanadium functionalized fibers were applied in a pseudo continuous flow set-up. Factors influencing the overall conversion and product selectivity, including flow rate and catalyst quantity, were investigated. At flow rates of 1–4 mL h−1 near quantitative conversion was maintained over an extended period. Keeping the mass of catalyst constant (0.025 g) and varying the flow rate from 1–6 mL h−1 resulted in a shift in the formation of the oxidation product methyl phenyl sulfone from 60.1 to 18.6%.
- Full Text:
- Date Issued: 2012
- Authors: Walmsley, Ryan S , Ogunlaja, Adeniyi S , Coombes, Matthew J , Chidawanyika, Wadzanai J U , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246041 , vital:51431 , xlink:href="https://doi.org/10.1039/C2JM15485D"
- Description: Both polymer microspheres and microfibers containing the imidazole functionality have been prepared and used to immobilize oxovanadium(IV). The average diameters and BET surface areas of the microspheres were 322 μm and 155 m2 g−1 while the fibers were 1.85 μm and 52 m2 g−1, respectively. XPS and microanalysis confirmed the incorporation of imidazole and vanadium in the polymeric materials. The catalytic activity of both materials was evaluated using the hydrogen peroxide facilitated oxidation of thioanisole. The microspheres were applied in a typical laboratory batch reactor set-up and quantitative conversions (>99%) were obtained in under 240 min with turn-over frequencies ranging from 21.89 to 265.53 h−1, depending on the quantity of catalyst and temperature. The microspherical catalysts also proved to be recyclable with no drop in activity being observed after three successive reactions. The vanadium functionalized fibers were applied in a pseudo continuous flow set-up. Factors influencing the overall conversion and product selectivity, including flow rate and catalyst quantity, were investigated. At flow rates of 1–4 mL h−1 near quantitative conversion was maintained over an extended period. Keeping the mass of catalyst constant (0.025 g) and varying the flow rate from 1–6 mL h−1 resulted in a shift in the formation of the oxidation product methyl phenyl sulfone from 60.1 to 18.6%.
- Full Text:
- Date Issued: 2012
In vitro photodynamic effect of aluminum tetrasulfophthalocyanines on melanoma skin cancer and healthy normal skin cells
- Maduray, Kaminee, Odhay, Bharti, Nyokong, Tebello
- Authors: Maduray, Kaminee , Odhay, Bharti , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245762 , vital:51403 , xlink:href="https://doi.org/10.1016/j.pdpdt.2011.07.001"
- Description: Photodynamic therapy is a medical treatment that uses an inactive dye/drug and lasers as a light source to activate the dye/drug to produce a toxic form of oxygen that destroys the cancer cells. This study aimed at investigating the cytotoxic effects of different concentrations of aluminum tetrasulfophthalocyanines in its inactive and active state (laser induced) on melanoma skin cancer cells, healthy normal skin fibroblast and keratinocyte cells. Experimentally, 3 x 10(4) cells/ml were seeded in 24-well plates before treatment with different concentrations of aluminum tetrasulfophthalocyanines. After 2 h, cells were irradiated with a light dose of 4.5 J/cm(2). Post-irradiated cells were incubated for 24 h before cell viability was measured using the CellTiter-Blue Viability Assay. Results showed that aluminum tetrasulfophthalocyanines at high concentrations were cytotoxic to melanoma cells in the absence of laser activation. In the presence of laser activation of aluminum tetrasulfophthalocyanines at a concentration of 40 mu g/ml decreased cell viability of melanoma cells to 45%, fibroblasts to 78% and keratinocytes to 73%. At this photosensitizing concentration of aluminum tetrasulfophthalocyanines the efficacy of the treatment light dose 4.5 J/cm(2) and the cell death mechanism induced by photoactivated aluminum tetrasulfophthalocyanines was evaluated. A light dose of 4.5 J/cm(2) was more efficient in killing a higher number of melanoma cells and a lower number of fibroblast and keratinocyte cells than the other light doses of 2.5 J/cm(2), 7.5 J/cm(2) and 10.5 J/cm(2). Apoptosis features such as blebbing, nucleus condensation, nucleus fragmentation and the formation of apoptotic bodies were seen in the photodynamic therapy treated melanoma skin cancer cells. This in vitro photodynamic therapy study concludes that using aluminum tetrasulfophthalocyanines at a photosensitizing concentration of 40 mu g/ml in combination with a laser dose of 4.5 J/cm(2) was potentially lethal for melanoma skin cancer cells and less harmful for the normal healthy skin cells. (c) 2011 Elsevier B.V. All rights reserved.
- Full Text:
- Date Issued: 2012
- Authors: Maduray, Kaminee , Odhay, Bharti , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245762 , vital:51403 , xlink:href="https://doi.org/10.1016/j.pdpdt.2011.07.001"
- Description: Photodynamic therapy is a medical treatment that uses an inactive dye/drug and lasers as a light source to activate the dye/drug to produce a toxic form of oxygen that destroys the cancer cells. This study aimed at investigating the cytotoxic effects of different concentrations of aluminum tetrasulfophthalocyanines in its inactive and active state (laser induced) on melanoma skin cancer cells, healthy normal skin fibroblast and keratinocyte cells. Experimentally, 3 x 10(4) cells/ml were seeded in 24-well plates before treatment with different concentrations of aluminum tetrasulfophthalocyanines. After 2 h, cells were irradiated with a light dose of 4.5 J/cm(2). Post-irradiated cells were incubated for 24 h before cell viability was measured using the CellTiter-Blue Viability Assay. Results showed that aluminum tetrasulfophthalocyanines at high concentrations were cytotoxic to melanoma cells in the absence of laser activation. In the presence of laser activation of aluminum tetrasulfophthalocyanines at a concentration of 40 mu g/ml decreased cell viability of melanoma cells to 45%, fibroblasts to 78% and keratinocytes to 73%. At this photosensitizing concentration of aluminum tetrasulfophthalocyanines the efficacy of the treatment light dose 4.5 J/cm(2) and the cell death mechanism induced by photoactivated aluminum tetrasulfophthalocyanines was evaluated. A light dose of 4.5 J/cm(2) was more efficient in killing a higher number of melanoma cells and a lower number of fibroblast and keratinocyte cells than the other light doses of 2.5 J/cm(2), 7.5 J/cm(2) and 10.5 J/cm(2). Apoptosis features such as blebbing, nucleus condensation, nucleus fragmentation and the formation of apoptotic bodies were seen in the photodynamic therapy treated melanoma skin cancer cells. This in vitro photodynamic therapy study concludes that using aluminum tetrasulfophthalocyanines at a photosensitizing concentration of 40 mu g/ml in combination with a laser dose of 4.5 J/cm(2) was potentially lethal for melanoma skin cancer cells and less harmful for the normal healthy skin cells. (c) 2011 Elsevier B.V. All rights reserved.
- Full Text:
- Date Issued: 2012
Interaction of CdTe quantum dots with 2, 2-diphenyl-1-picrylhydrazyl free radical
- Adegoke, Oluwasesan, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245751 , vital:51402 , xlink:href="https://doi.org/10.1007/s10895-011-1012-2"
- Description: The interaction of 2,2-diphenyl-1-picrylhydrazyl (DPPH●) free radical with thiol-capped CdTe quantum dots (QDs) has been studied by UV–vis spectroscopy, steady state and time resolved fluorescence measurements. Addition of DPPH● radical to CdTe QDs resulted in fluorescence quenching. The interaction occurs through static quenching as this was confirmed by fluorescence lifetime measurements. Time course absorption studies indicates that DPPH● may be reduced by interaction with QDs to the substituted hydrazine form (2,2-diphenyl-1-picrylhydrazine) DPPH-H. The mechanism of fluorescence quenching of CdTe QDs by DPPH● is proposed.
- Full Text:
- Date Issued: 2012
- Authors: Adegoke, Oluwasesan , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245751 , vital:51402 , xlink:href="https://doi.org/10.1007/s10895-011-1012-2"
- Description: The interaction of 2,2-diphenyl-1-picrylhydrazyl (DPPH●) free radical with thiol-capped CdTe quantum dots (QDs) has been studied by UV–vis spectroscopy, steady state and time resolved fluorescence measurements. Addition of DPPH● radical to CdTe QDs resulted in fluorescence quenching. The interaction occurs through static quenching as this was confirmed by fluorescence lifetime measurements. Time course absorption studies indicates that DPPH● may be reduced by interaction with QDs to the substituted hydrazine form (2,2-diphenyl-1-picrylhydrazine) DPPH-H. The mechanism of fluorescence quenching of CdTe QDs by DPPH● is proposed.
- Full Text:
- Date Issued: 2012
Layer by Layer Electrode Surface Functionalisation Using Carbon Nanotubes, Electrochemical Grafting of Azide‐Alkyne Functions and Click Chemistry
- Coates, Megan, Griveau, Sophie, Bedioui, Fethi, Nyokong, Tebello
- Authors: Coates, Megan , Griveau, Sophie , Bedioui, Fethi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243509 , vital:51159 , xlink:href="https://doi.org/10.1002/elan.201200240"
- Description: Ferrocene was covalently bonded to a layer of adsorbed single-walled carbon nanotubes on a glassy carbon electrode surface using electrochemical grafting and click chemistry. Grafting of the 4-azidobenzenediazonium salt onto the surface was accomplished by electrochemical reduction. The surface-bound azide groups, with the use of a copper(I) catalyst, were reacted with ethynylferrocene to form covalent 1,2,3-triazole bonds by click chemistry. This layer by layer construction of the electrode surface results in stable electrodes by combining good electrical conductivity and increased surface area of the nanotubes with the versatility of the Sharpless click reaction.
- Full Text:
- Date Issued: 2012
- Authors: Coates, Megan , Griveau, Sophie , Bedioui, Fethi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243509 , vital:51159 , xlink:href="https://doi.org/10.1002/elan.201200240"
- Description: Ferrocene was covalently bonded to a layer of adsorbed single-walled carbon nanotubes on a glassy carbon electrode surface using electrochemical grafting and click chemistry. Grafting of the 4-azidobenzenediazonium salt onto the surface was accomplished by electrochemical reduction. The surface-bound azide groups, with the use of a copper(I) catalyst, were reacted with ethynylferrocene to form covalent 1,2,3-triazole bonds by click chemistry. This layer by layer construction of the electrode surface results in stable electrodes by combining good electrical conductivity and increased surface area of the nanotubes with the versatility of the Sharpless click reaction.
- Full Text:
- Date Issued: 2012
Like a bolt from the blue : phthalocyanines in biomedical optics
- Sekkat, N, Van den Berg, H, Nyokong, Tebello, Lange, N
- Authors: Sekkat, N , Van den Berg, H , Nyokong, Tebello , Lange, N
- Date: 2012
- Subjects: Biomedical optics Fluorescence diagnosis Phthalocyanines NIR dyes Photodynamic therapy
- Language: English
- Type: Article
- Identifier: vital:6597 , http://hdl.handle.net/10962/d1004346 , http://dx.doi.org/10.3390/molecules17010098
- Description: The purpose of this review is to compile preclinical and clinical results on phthalocyanines (Pcs) as photosensitizers (PS) for Photodynamic Therapy (PDT) and contrast agents for fluorescence imaging. Indeed, Pcs are excellent candidates in these fields due to their strong absorbance in the NIR region and high chemical and photo-stability. In particular, this is mostly relevant for their in vivo activation in deeper tissular regions. However, most Pcs present two major limitations, i.e., a strong tendency to aggregate and a low water-solubility. In order to overcome these issues, both chemical tuning and pharmaceutical formulation combined with tumor targeting strategies were applied. These aspects will be developed in this review for the most extensively studied Pcs during the last 25 years, i.e., aluminium-, zinc- and silicon-based Pcs.
- Full Text:
- Date Issued: 2012
- Authors: Sekkat, N , Van den Berg, H , Nyokong, Tebello , Lange, N
- Date: 2012
- Subjects: Biomedical optics Fluorescence diagnosis Phthalocyanines NIR dyes Photodynamic therapy
- Language: English
- Type: Article
- Identifier: vital:6597 , http://hdl.handle.net/10962/d1004346 , http://dx.doi.org/10.3390/molecules17010098
- Description: The purpose of this review is to compile preclinical and clinical results on phthalocyanines (Pcs) as photosensitizers (PS) for Photodynamic Therapy (PDT) and contrast agents for fluorescence imaging. Indeed, Pcs are excellent candidates in these fields due to their strong absorbance in the NIR region and high chemical and photo-stability. In particular, this is mostly relevant for their in vivo activation in deeper tissular regions. However, most Pcs present two major limitations, i.e., a strong tendency to aggregate and a low water-solubility. In order to overcome these issues, both chemical tuning and pharmaceutical formulation combined with tumor targeting strategies were applied. These aspects will be developed in this review for the most extensively studied Pcs during the last 25 years, i.e., aluminium-, zinc- and silicon-based Pcs.
- Full Text:
- Date Issued: 2012
Molecular catalysis of the oxygen reduction reaction by iron porphyrin catalysts tethered into Nafion layers
- He, Qinggang, Mugadza, Tawanda, Kang, Xiongwu, Zhu, Xiaobing, Chen, Shaowei, Kerr, John, Nyokong, Tebello
- Authors: He, Qinggang , Mugadza, Tawanda , Kang, Xiongwu , Zhu, Xiaobing , Chen, Shaowei , Kerr, John , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243168 , vital:51123 , xlink:href="https://doi.org/10.1016/j.jpowsour.2012.05.043"
- Description: This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV–Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.
- Full Text:
- Date Issued: 2012
- Authors: He, Qinggang , Mugadza, Tawanda , Kang, Xiongwu , Zhu, Xiaobing , Chen, Shaowei , Kerr, John , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243168 , vital:51123 , xlink:href="https://doi.org/10.1016/j.jpowsour.2012.05.043"
- Description: This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV–Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.
- Full Text:
- Date Issued: 2012
Oxovanadium (IV)-catalysed oxidation of dibenzothiophene and 4, 6-dimethyldibenzothiophene
- Ogunlaja, Adeniyi S, Chidawanyika, Wadzanai J U, Antunes, Edith M, Fernandes, Manuel A, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
- Full Text:
- Date Issued: 2012
- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
- Full Text:
- Date Issued: 2012
Photooxidation of 4-chlorophenol sensitized by lutetium tetraphenoxy phthalocyanine anchored on electrospun polystyrene polymer fiber
- Zugle, Ruphino, Antunes, Edith M, Khene, Samson M, Nyokong, Tebello
- Authors: Zugle, Ruphino , Antunes, Edith M , Khene, Samson M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245787 , vital:51405 , xlink:href="https://doi.org/10.1016/j.poly.2011.11.005"
- Description: An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.
- Full Text:
- Date Issued: 2012
- Authors: Zugle, Ruphino , Antunes, Edith M , Khene, Samson M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245787 , vital:51405 , xlink:href="https://doi.org/10.1016/j.poly.2011.11.005"
- Description: An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.
- Full Text:
- Date Issued: 2012
Photophysical and photochemical properties of novel phthalocyanines bearing non-peripherally substituted mercaptoquinoline moiety
- Yaşa, Göknur, Erdoğmuş, Ali, Uğur, Ahmet Lütf, Şener, M Kasım, Avcıata, Ulvi, Nyokong, Tebello
- Authors: Yaşa, Göknur , Erdoğmuş, Ali , Uğur, Ahmet Lütf , Şener, M Kasım , Avcıata, Ulvi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244360 , vital:51250 , xlink:href="https://doi.org/10.1142/S1088424612500940"
- Description: The synthesis, photophysical and photochemical properties of nonperipherally (a) mercaptoquinoline substituted Zn(II), TiO(IV) and Mg(II) and quaternized Zn(II) phthalocyanines are described for the first time. These complexes (2 to 5) and their precursor are characterized by elemental analysis, FT-IR, 1 H NMR, electronic spectroscopy as well as mass spectroscopy. Complexes 2, 4 and 5 have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated in all solvents within a wide concentration range. Complex 3 showed very good solubility in water as well as DMSO and DMF. General trends are described for singlet oxygen, photodegradation and fluorescence quantum yields of these complexes in DMSO and DMF. While complex 2 has higher singlet oxygen and fluorescence quantum yields than 3, 4 and 5, complex 4 has higher fluorescence quantum yields in DMF and DMSO than 2, 3 and 5. The effect of the solvents and metal on the photophysical and photochemical parameters of the metallophthalocyanines are also reported.
- Full Text:
- Date Issued: 2012
- Authors: Yaşa, Göknur , Erdoğmuş, Ali , Uğur, Ahmet Lütf , Şener, M Kasım , Avcıata, Ulvi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244360 , vital:51250 , xlink:href="https://doi.org/10.1142/S1088424612500940"
- Description: The synthesis, photophysical and photochemical properties of nonperipherally (a) mercaptoquinoline substituted Zn(II), TiO(IV) and Mg(II) and quaternized Zn(II) phthalocyanines are described for the first time. These complexes (2 to 5) and their precursor are characterized by elemental analysis, FT-IR, 1 H NMR, electronic spectroscopy as well as mass spectroscopy. Complexes 2, 4 and 5 have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated in all solvents within a wide concentration range. Complex 3 showed very good solubility in water as well as DMSO and DMF. General trends are described for singlet oxygen, photodegradation and fluorescence quantum yields of these complexes in DMSO and DMF. While complex 2 has higher singlet oxygen and fluorescence quantum yields than 3, 4 and 5, complex 4 has higher fluorescence quantum yields in DMF and DMSO than 2, 3 and 5. The effect of the solvents and metal on the photophysical and photochemical parameters of the metallophthalocyanines are also reported.
- Full Text:
- Date Issued: 2012
Photophysical and photochemical studies of sulfur containing phthalocyanine derivatives in the presence of folic acid
- Nombona, Nolwazi, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243180 , vital:51124 , xlink:href="https://doi.org/10.1016/j.ica.2012.03.051"
- Description: The syntheses of zinc and magnesium 9,16,23-tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyaninato complexes are described for the first time. The photophysical and photochemical parameters of these molecules in the absence or presence of folic acid are compared to the corresponding oxygen bridged complexes and to 2,9,17,23-tetrakis-[(1,6-hexanedithiol)phthalocyaninato]zinc(II), [8,15,22-tris-(naptho)-2-(amidoethanethiol)phthalocyaninato]zinc(II) and zinc phthalocyanine tetrasulfonate. In the absence of folic acid, the complexes show relatively good triplet quantum yields (ranging from 0.52 to 0.88) in DMSO with reasonable triplet lifetime between 140 and 470 μs. The complexes showed high singlet oxygen quantum yield values ranging from 0.27 to 0.66 in the absence of folic acid. In the presence of folic acid, the triplet quantum yield values were between 0.37 and 0.75 and the lifetimes were significantly reduced (70–320 μs).
- Full Text:
- Date Issued: 2012
- Authors: Nombona, Nolwazi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243180 , vital:51124 , xlink:href="https://doi.org/10.1016/j.ica.2012.03.051"
- Description: The syntheses of zinc and magnesium 9,16,23-tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyaninato complexes are described for the first time. The photophysical and photochemical parameters of these molecules in the absence or presence of folic acid are compared to the corresponding oxygen bridged complexes and to 2,9,17,23-tetrakis-[(1,6-hexanedithiol)phthalocyaninato]zinc(II), [8,15,22-tris-(naptho)-2-(amidoethanethiol)phthalocyaninato]zinc(II) and zinc phthalocyanine tetrasulfonate. In the absence of folic acid, the complexes show relatively good triplet quantum yields (ranging from 0.52 to 0.88) in DMSO with reasonable triplet lifetime between 140 and 470 μs. The complexes showed high singlet oxygen quantum yield values ranging from 0.27 to 0.66 in the absence of folic acid. In the presence of folic acid, the triplet quantum yield values were between 0.37 and 0.75 and the lifetimes were significantly reduced (70–320 μs).
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- Date Issued: 2012