Synthesis, photophysical and photochemical properties of novel soluble tetra [4-(thiophen-3yl)-phenoxy] phthalocyaninato zinc (II) and Ti (IV) O complexes
- Erdoğmuş, Ali, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263318 , vital:53617 , xlink:href="https://doi.org/10.1016/j.ica.2009.07.015"
- Description: The synthesis, photophysical and photochemical properties of zinc and oxo-titanium phthalocyanine derivatives 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)zinc(II), (2); and 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)oxo-titanium(IV), (3), are described for the first time. These peripherally substituted complexes (2 and 3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic spectroscopy. The compounds (2 and 3) have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO, DMF and THF. Compound 2 has higher fluorescence quantum yields, triplet quantum yields and triplet life times than 3, however, the former has lower singlet oxygen quantum yields and photodegradation quantum yields than the latter.
- Full Text:
- Date Issued: 2009
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263318 , vital:53617 , xlink:href="https://doi.org/10.1016/j.ica.2009.07.015"
- Description: The synthesis, photophysical and photochemical properties of zinc and oxo-titanium phthalocyanine derivatives 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)zinc(II), (2); and 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)oxo-titanium(IV), (3), are described for the first time. These peripherally substituted complexes (2 and 3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic spectroscopy. The compounds (2 and 3) have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO, DMF and THF. Compound 2 has higher fluorescence quantum yields, triplet quantum yields and triplet life times than 3, however, the former has lower singlet oxygen quantum yields and photodegradation quantum yields than the latter.
- Full Text:
- Date Issued: 2009
The photobleaching of the free and encapsulated metallic phthalocyanine and its effect on the photooxidation of simple molecules
- Fanchiotti, Brenda Gomes, Machado, Marcella Piffer Zamprogno, de Paula, Letícia Camilato, Durmuş, Mahmut, Nyokong, Tebello, da Silva, Gonçalves, da Silva, André Romero
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2016
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2016
A comparative photophysicochemical study of mono substituted phthalocyanines grafted onto silica nanoparticles
- Fashina, Adebayo, Antunes, Edith M, Nyokong, Tebello
- Authors: Fashina, Adebayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193844 , vital:45399 , xlink:href="https://doi.org/10.1142/S1088424614500138"
- Description: In this study, we report on the covalent linking of carboxylic acid functionalized silica nanoparticles with zinc phthalocyanine mono-substituted non-peripherally and peripherally with either a 4-amino phenoxy (1, peripheral and 2, non-peripheral) or an amino group (3 peripheral). The grafting is achieved via the formation of an amide bond between the carboxylic acid of the silica nanoparticles and the amino group of the phthalocyanine complexes. The hybrid nanoparticles retained the amorphous nature of silica nanoparticles after conjugation. A slight decrease in fluorescence and a general improvement in triplet quantum yields compared to free Pcs were observed. Triplet lifetimes for 2-SiNPs and 3-SiNPs also improved when compared to the free phthalocyanine. The changes in singlet oxygen quantum yields upon conjugation were minimal.
- Full Text:
- Date Issued: 2014
- Authors: Fashina, Adebayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193844 , vital:45399 , xlink:href="https://doi.org/10.1142/S1088424614500138"
- Description: In this study, we report on the covalent linking of carboxylic acid functionalized silica nanoparticles with zinc phthalocyanine mono-substituted non-peripherally and peripherally with either a 4-amino phenoxy (1, peripheral and 2, non-peripheral) or an amino group (3 peripheral). The grafting is achieved via the formation of an amide bond between the carboxylic acid of the silica nanoparticles and the amino group of the phthalocyanine complexes. The hybrid nanoparticles retained the amorphous nature of silica nanoparticles after conjugation. A slight decrease in fluorescence and a general improvement in triplet quantum yields compared to free Pcs were observed. Triplet lifetimes for 2-SiNPs and 3-SiNPs also improved when compared to the free phthalocyanine. The changes in singlet oxygen quantum yields upon conjugation were minimal.
- Full Text:
- Date Issued: 2014
Silica nanoparticles grafted with phthalocyanines
- Fashina, Adebayo, Antunes, Edith M, Nyokong, Tebello
- Authors: Fashina, Adebayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232545 , vital:50001 , xlink:href="https://doi.org/10.1039/C3NJ00439B"
- Description: Silica nanoparticles grafted with phthalocyanines (tetra-substituted non-peripherally with 4-carboxyphenoxy and 3-carboxyphenoxy groups) have been synthesized, characterized and their photophysical properties evaluated in solution. The phthalocyanine dyes have a free carboxyl group facilitating the covalent attachment of the dye onto the silica surface via ester bond formation. The photophysical properties of the hybrid nanoparticles show higher fluorescence and triplet quantum yields as well as longer triplet lifetimes as compared to the free phthalocyanines. The triplet quantum yields were found to be higher for the phthalocyanines with ester bonds as compared to the amide bonded linkages. The silica nanoparticles were also studied in artificial lysosomal fluid over a period of 96 h and the dissolution of the nanoparticles was monitored and confirmed using inductively coupled plasma optical emission spectrometry.
- Full Text:
- Date Issued: 2013
- Authors: Fashina, Adebayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232545 , vital:50001 , xlink:href="https://doi.org/10.1039/C3NJ00439B"
- Description: Silica nanoparticles grafted with phthalocyanines (tetra-substituted non-peripherally with 4-carboxyphenoxy and 3-carboxyphenoxy groups) have been synthesized, characterized and their photophysical properties evaluated in solution. The phthalocyanine dyes have a free carboxyl group facilitating the covalent attachment of the dye onto the silica surface via ester bond formation. The photophysical properties of the hybrid nanoparticles show higher fluorescence and triplet quantum yields as well as longer triplet lifetimes as compared to the free phthalocyanines. The triplet quantum yields were found to be higher for the phthalocyanines with ester bonds as compared to the amide bonded linkages. The silica nanoparticles were also studied in artificial lysosomal fluid over a period of 96 h and the dissolution of the nanoparticles was monitored and confirmed using inductively coupled plasma optical emission spectrometry.
- Full Text:
- Date Issued: 2013
Photophysical behavior of Zn aminophenoxy substituted phthalocyanine conjugates with carboxylic acid-coated silica nanoparticles
- Fashina, Adedayo, Antunes, Edith M, Nyokong, Tebello
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193802 , vital:45397 , xlink:href="https://doi.org/10.1016/j.molstruc.2014.04.034"
- Description: This work reports on the grafting of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally and peripherally with a 4-amino phenoxy group. The phthalocyanine dyes have free amino groups, facilitating covalent attachment of the dyes on the silica surface via amide bond formation. The surface area of the functionalized silica nanoparticles increased on conjugation but the pore volumes were reduced. The phthalocyanine functionalized silica nanoparticles showed lower fluorescence quantum yields as well as shorter triplet lifetimes compared to the free phthalocyanines in dimethyl formamide. For the non-peripherally substituted phthalocyanines increases in triplet yield quantum yields, lifetimes, and singlet oxygen quantum yields were observed.
- Full Text:
- Date Issued: 2014
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193802 , vital:45397 , xlink:href="https://doi.org/10.1016/j.molstruc.2014.04.034"
- Description: This work reports on the grafting of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally and peripherally with a 4-amino phenoxy group. The phthalocyanine dyes have free amino groups, facilitating covalent attachment of the dyes on the silica surface via amide bond formation. The surface area of the functionalized silica nanoparticles increased on conjugation but the pore volumes were reduced. The phthalocyanine functionalized silica nanoparticles showed lower fluorescence quantum yields as well as shorter triplet lifetimes compared to the free phthalocyanines in dimethyl formamide. For the non-peripherally substituted phthalocyanines increases in triplet yield quantum yields, lifetimes, and singlet oxygen quantum yields were observed.
- Full Text:
- Date Issued: 2014
A comparative photophysicochemical study of phthalocyanines encapsulated in core–shell silica nanoparticles
- Fashina, Adedayo, Amuhaya, Edith, Nyokong, Tebello
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189708 , vital:44924 , xlink:href="https://doi.org/10.1016/j.saa.2014.08.062"
- Description: This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4- carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix.
- Full Text:
- Date Issued: 2015
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189708 , vital:44924 , xlink:href="https://doi.org/10.1016/j.saa.2014.08.062"
- Description: This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4- carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix.
- Full Text:
- Date Issued: 2015
Photophysical studies of newly derivatized mono substituted phthalocyanines grafted onto silica nanoparticles via click chemistry
- Fashina, Adedayo, Amuhaya, Edith, Nyokong, Tebello
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189537 , vital:44855 , xlink:href="https://doi.org/10.1016/j.saa.2014.12.070"
- Description: This work reports on the synthesis, characterization and photophysical studies of newly derived phthalocyanine complexes and the phthalocyanine–silica nanoparticles conjugates. The derived phthalocyanine complexes have one terminal alkyne group. The derived phthalocyanine complexes showed improved photophysical properties (ФF, ФT, ΦΔ and τT) compared to the respective phthalocyanine complexes from which they were derived. The derived phthalocyanine complexes were conjugated to the surface of an azide functionalized silica nanoparticles via copper (1) catalyzed cyclo-addition reaction. All the conjugates showed lower triplet quantum yields ranging from 0.37 to 0.44 compared to the free phthalocyanine complexes. The triplet lifetimes ranged from 352 to 484 μs for the conjugates and from 341 to 366 μs for the free phthalocyanine complexes.
- Full Text:
- Date Issued: 2015
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189537 , vital:44855 , xlink:href="https://doi.org/10.1016/j.saa.2014.12.070"
- Description: This work reports on the synthesis, characterization and photophysical studies of newly derived phthalocyanine complexes and the phthalocyanine–silica nanoparticles conjugates. The derived phthalocyanine complexes have one terminal alkyne group. The derived phthalocyanine complexes showed improved photophysical properties (ФF, ФT, ΦΔ and τT) compared to the respective phthalocyanine complexes from which they were derived. The derived phthalocyanine complexes were conjugated to the surface of an azide functionalized silica nanoparticles via copper (1) catalyzed cyclo-addition reaction. All the conjugates showed lower triplet quantum yields ranging from 0.37 to 0.44 compared to the free phthalocyanine complexes. The triplet lifetimes ranged from 352 to 484 μs for the conjugates and from 341 to 366 μs for the free phthalocyanine complexes.
- Full Text:
- Date Issued: 2015
Characterization and photophysical behavior of phthalocyanines when grafted onto silica nanoparticles
- Fashina, Adedayo, Antunes, Edith M, Nyokong, Tebello
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241981 , vital:50989 , xlink:href="https://doi.org/10.1016/j.poly.2013.01.037"
- Description: This work reports on the functionalization of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally with 4-carboxyphenoxyl and 3-carboxyphenoxyl groups. The phthalocyanine dyes have a free carboxyl group, facilitating the covalent attachment of the dyes on the silica surface via amide bond formation. The phthalocyanine functionalized silica nanoparticles showed higher fluorescence and triplet quantum yields as well as longer triplet lifetimes compared to the free phthalocyanines.
- Full Text:
- Date Issued: 2013
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241981 , vital:50989 , xlink:href="https://doi.org/10.1016/j.poly.2013.01.037"
- Description: This work reports on the functionalization of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally with 4-carboxyphenoxyl and 3-carboxyphenoxyl groups. The phthalocyanine dyes have a free carboxyl group, facilitating the covalent attachment of the dyes on the silica surface via amide bond formation. The phthalocyanine functionalized silica nanoparticles showed higher fluorescence and triplet quantum yields as well as longer triplet lifetimes compared to the free phthalocyanines.
- Full Text:
- Date Issued: 2013
Adsorption and separation of platinum and palladium by polyamine functionalized polystyrene-based beads and nanofibers
- Fayemi, Omolola E, Ogunlaja, Adeniyi S, Kempgens, Pierre F M, Antunes, Edith M, Torto, Nelson, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Kempgens, Pierre F M , Antunes, Edith M , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241694 , vital:50961 , xlink:href="https://doi.org/10.1016/j.mineng.2013.06.006"
- Description: Adsorption and separation of platinum and palladium chlorido species (PtCl62- and PdCl42-) on polystyrene beads as well as nanofibers functionalized with ammonium centres based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and tris-(2-aminoethyl)amine (TAEA) are described. The functionalized sorbent materials were characterized by microanalysis, SEM, XPS, BET and FTIR. The surface area of the functionalized fibers was in the range 69–241 m2/g while it was 73–107 m2/g for the beads. The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies at 1 M HCl concentration. The adsorption studies for both PtCl62- and PdCl42- on the different sorbent materials fit the Langmuir isotherm with R2 values >0.99. The highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively for the nanofiber sorbent material based on ethylenediamine (EDA) while the beads with ethylenediamine (EDA) gave 1.0 mg/g and 0.2 mg/g for Pt and Pd respectively. Metals loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as the eluting agent with quantitative desorption efficiency under the selected experimental conditions. Separation of platinum from palladium was partially achieved by selective stripping of PtCl62- with 0.5 M of NaClO4 in 1.0 M HCl while PdCl42- was eluted with 0.5 M thiourea in 1.0 M HCl. Separation of platinum from iridium and rhodium under 1 M HCl concentration was successful on triethylenetriamine (TETA)-functionalized Merrifield beads. This material (M-TETA) showed selectivity for platinum albeit the low loading capacity.
- Full Text:
- Date Issued: 2013
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Kempgens, Pierre F M , Antunes, Edith M , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241694 , vital:50961 , xlink:href="https://doi.org/10.1016/j.mineng.2013.06.006"
- Description: Adsorption and separation of platinum and palladium chlorido species (PtCl62- and PdCl42-) on polystyrene beads as well as nanofibers functionalized with ammonium centres based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and tris-(2-aminoethyl)amine (TAEA) are described. The functionalized sorbent materials were characterized by microanalysis, SEM, XPS, BET and FTIR. The surface area of the functionalized fibers was in the range 69–241 m2/g while it was 73–107 m2/g for the beads. The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies at 1 M HCl concentration. The adsorption studies for both PtCl62- and PdCl42- on the different sorbent materials fit the Langmuir isotherm with R2 values >0.99. The highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively for the nanofiber sorbent material based on ethylenediamine (EDA) while the beads with ethylenediamine (EDA) gave 1.0 mg/g and 0.2 mg/g for Pt and Pd respectively. Metals loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as the eluting agent with quantitative desorption efficiency under the selected experimental conditions. Separation of platinum from palladium was partially achieved by selective stripping of PtCl62- with 0.5 M of NaClO4 in 1.0 M HCl while PdCl42- was eluted with 0.5 M thiourea in 1.0 M HCl. Separation of platinum from iridium and rhodium under 1 M HCl concentration was successful on triethylenetriamine (TETA)-functionalized Merrifield beads. This material (M-TETA) showed selectivity for platinum albeit the low loading capacity.
- Full Text:
- Date Issued: 2013
The development of palladium (II)-specific amine-functionalized silica-based microparticles
- Fayemi, Omolola E, Ogunlaja, Adeniyi S, Antunes, Edith M, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241083 , vital:50903 , xlink:href="https://doi.org/10.1080/01496395.2014.978017"
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources.
- Full Text:
- Date Issued: 2015
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241083 , vital:50903 , xlink:href="https://doi.org/10.1080/01496395.2014.978017"
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources.
- Full Text:
- Date Issued: 2015
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
Redox reactions of an Mo (V) tetrasulfophthalocyanine
- Ferraudi, Guillermo, Nyokong, Tebello, Feliz, Mario, Perkovic, Marc, Rillema, D Paul
- Authors: Ferraudi, Guillermo , Nyokong, Tebello , Feliz, Mario , Perkovic, Marc , Rillema, D Paul
- Date: 1994
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295530 , vital:57351 , xlink:href="https://doi.org/10.1016/0020-1693(93)03664-V"
- Description: The preparation of an Mo(V) tetrasulfophthalocyanine and some of its thermal and photochemical reactions have been investigated in this work. Electrochemical processes have been followed by means of the UVVis spectral changes and compared with those observed in flash photolysis. Mo(IV) and Mo(V)-ligand-radical species are common intermediates of the electrochemical and photochemical reactions. In 254 nm irradiations of the Mo(V) tetrasulfophthalocyanine in aqueous solutions of 2-propanol, the macrocycle can be photohydrogenated and the product of the photolysis can be reoxidized with O2 back to the parent complex.
- Full Text:
- Date Issued: 1994
- Authors: Ferraudi, Guillermo , Nyokong, Tebello , Feliz, Mario , Perkovic, Marc , Rillema, D Paul
- Date: 1994
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295530 , vital:57351 , xlink:href="https://doi.org/10.1016/0020-1693(93)03664-V"
- Description: The preparation of an Mo(V) tetrasulfophthalocyanine and some of its thermal and photochemical reactions have been investigated in this work. Electrochemical processes have been followed by means of the UVVis spectral changes and compared with those observed in flash photolysis. Mo(IV) and Mo(V)-ligand-radical species are common intermediates of the electrochemical and photochemical reactions. In 254 nm irradiations of the Mo(V) tetrasulfophthalocyanine in aqueous solutions of 2-propanol, the macrocycle can be photohydrogenated and the product of the photolysis can be reoxidized with O2 back to the parent complex.
- Full Text:
- Date Issued: 1994
Critical assessment of the quartz crystal microbalance with dissipation as an analytical tool for biosensor development and fundamental studies
- Fogel, Ronen, Mashazi, Philani N, Nyokong, Tebello, Limson, Janice
- Authors: Fogel, Ronen , Mashazi, Philani N , Nyokong, Tebello , Limson, Janice
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271204 , vital:54521 , xlink:href="https://doi.org/10.1016/j.bios.2007.03.012"
- Description: One of the challenges in electrochemical biosensor design is gaining a fundamental knowledge of the processes underlying immobilisation of the molecules onto the electrode surface. This is of particular importance in biocomposite sensors where concerns have arisen as to the nature of the interaction between the biological and synthetic molecules immobilised. We examined the use of the Quartz Crystal Microbalance with Dissipation (QCM-D) as a tool for fundamental analyses of a model sensor constructed by the immobilisation of cobalt(II) phthalocyanine (TCACoPc) and glucose oxidase (GOx) onto a gold-quartz electrode (electrode surface) for the enhanced detection of glucose. The model sensor was constructed in aqueous phase and covalently linked the gold surface to the TCACoPc, and the TCACoPc to the GOx, using the QCM-D. The aqueous metallophthalocyanine (MPc) formed a multi-layer over the surface of the electrode, which could be removed to leave a monolayer with a mass loading that compared favourably to the theoretical value expected. Analysis of frequency and dissipation plots indicated covalent attachment of glucose oxidase onto the metallophthalocyanine layer. The amount of GOx bound using the model system compared favourably to calculations derived from the maximal amperometric functioning of the electrochemical sensor (examined in previously-published literature, Mashazi, P.N., Ozoemena, K.I., Nyokong, T., 2006. Electrochim. Acta 52, 177–186), but not to theoretical values derived from dimensions of GOx as established by crystallography. The strength of the binding of the GOx film with the TCACoPc layer was tested by using 2% SDS as a denaturant/surfactant, and the GOx film was not found to be significantly affected by exposure to this. This paper thus showed that QCM-D can be used in order to model essential processes and interactions that dictate the functional parameters of a biosensor.
- Full Text:
- Date Issued: 2007
- Authors: Fogel, Ronen , Mashazi, Philani N , Nyokong, Tebello , Limson, Janice
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271204 , vital:54521 , xlink:href="https://doi.org/10.1016/j.bios.2007.03.012"
- Description: One of the challenges in electrochemical biosensor design is gaining a fundamental knowledge of the processes underlying immobilisation of the molecules onto the electrode surface. This is of particular importance in biocomposite sensors where concerns have arisen as to the nature of the interaction between the biological and synthetic molecules immobilised. We examined the use of the Quartz Crystal Microbalance with Dissipation (QCM-D) as a tool for fundamental analyses of a model sensor constructed by the immobilisation of cobalt(II) phthalocyanine (TCACoPc) and glucose oxidase (GOx) onto a gold-quartz electrode (electrode surface) for the enhanced detection of glucose. The model sensor was constructed in aqueous phase and covalently linked the gold surface to the TCACoPc, and the TCACoPc to the GOx, using the QCM-D. The aqueous metallophthalocyanine (MPc) formed a multi-layer over the surface of the electrode, which could be removed to leave a monolayer with a mass loading that compared favourably to the theoretical value expected. Analysis of frequency and dissipation plots indicated covalent attachment of glucose oxidase onto the metallophthalocyanine layer. The amount of GOx bound using the model system compared favourably to calculations derived from the maximal amperometric functioning of the electrochemical sensor (examined in previously-published literature, Mashazi, P.N., Ozoemena, K.I., Nyokong, T., 2006. Electrochim. Acta 52, 177–186), but not to theoretical values derived from dimensions of GOx as established by crystallography. The strength of the binding of the GOx film with the TCACoPc layer was tested by using 2% SDS as a denaturant/surfactant, and the GOx film was not found to be significantly affected by exposure to this. This paper thus showed that QCM-D can be used in order to model essential processes and interactions that dictate the functional parameters of a biosensor.
- Full Text:
- Date Issued: 2007
One-pot synthesis of graphene quantum dots–phthalocyanines supramolecular hybrid and the investigation of their photophysical properties
- Fomo, Gertrude, Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Fomo, Gertrude , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188126 , vital:44725 , xlink:href="https://doi.org/10.1007/s10853-017-1539-y"
- Description: The synthesis of graphene quantum dots (GQDs) using organic compounds as carbon sources via bottom-up approaches has been widely developed, whereas their hybrids with other materials have been previously achieved post-synthetically via multi-step procedures. A novel approach for the preparation of supramolecular hybrid conjugates of GQDs and phthalocyanines (Pcs) via an in situ one-step bottom-up route was employed in this study. The as-synthesized GQDs and their Pc conjugates were characterized using different spectroscopic techniques and their photophysicochemical properties evaluated. Notably, the singlet oxygen quantum yields of the Pcs in the presence of GQDs were found to be 0.51 and 0.74 for 1-GQDs and 2-GQDs, respectively, as compared to the Pcs alone (0.18 and 0.70 for complex 1 and 2, respectively). The increase in triplet quantum yield (ΦT) values is complemented by a decrease in fluorescence quantum yield (ΦF). ΦT value of 0.96 obtained for the complex 2 after conjugation with GQDs is better or higher than the value of 0.74 as reported in the literature when complex 2 was conjugated to semiconductor QDs. Hence, this novel approach resulted in the derivation of hybrid materials with potentials for various photophysicochemical applications such as photodynamic therapy and photocatalysis.
- Full Text:
- Date Issued: 2018
- Authors: Fomo, Gertrude , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188126 , vital:44725 , xlink:href="https://doi.org/10.1007/s10853-017-1539-y"
- Description: The synthesis of graphene quantum dots (GQDs) using organic compounds as carbon sources via bottom-up approaches has been widely developed, whereas their hybrids with other materials have been previously achieved post-synthetically via multi-step procedures. A novel approach for the preparation of supramolecular hybrid conjugates of GQDs and phthalocyanines (Pcs) via an in situ one-step bottom-up route was employed in this study. The as-synthesized GQDs and their Pc conjugates were characterized using different spectroscopic techniques and their photophysicochemical properties evaluated. Notably, the singlet oxygen quantum yields of the Pcs in the presence of GQDs were found to be 0.51 and 0.74 for 1-GQDs and 2-GQDs, respectively, as compared to the Pcs alone (0.18 and 0.70 for complex 1 and 2, respectively). The increase in triplet quantum yield (ΦT) values is complemented by a decrease in fluorescence quantum yield (ΦF). ΦT value of 0.96 obtained for the complex 2 after conjugation with GQDs is better or higher than the value of 0.74 as reported in the literature when complex 2 was conjugated to semiconductor QDs. Hence, this novel approach resulted in the derivation of hybrid materials with potentials for various photophysicochemical applications such as photodynamic therapy and photocatalysis.
- Full Text:
- Date Issued: 2018
Low symmetric metallophthalocyanine modified electrode via click chemistry for simultaneous detection of heavy metals
- Fomo, Gertrude, Nwaji, Njemuwa, Nyokong, Tebello
- Authors: Fomo, Gertrude , Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187914 , vital:44709 , xlink:href="https://doi.org/10.1016/j.jelechem.2018.02.016"
- Description: Beside different methods and materials used to develop electrochemical sensors, the modification of the electrode using click reaction based on metallophthalocyanine (MPc) compounds are shown to improve the stability and sensitivity of the sensor. This work reported the development of electrochemical sensor for mercury (II), Lead (II), copper (II) and cadmium (II) ions detection based on the synthesized novel low symmetry alkyne terminated cobalt Phthalocyanine (CoPc) derivative. Differential pulse stripping voltammetry (DPSV) technique was employed for the first time in simultaneous determination of trace levels of the above metal ions using modified glassy carbon electrode (GCE) via click chemistry. Under the optimum experimental conditions, the anodic peak current is proportional to the concentrations of metal ions over a wide range of 0 to 0.1 mM with nanolevel detection limit of 81.94, 327.71, 55.87 and 347.06 nM and the sensitivity of 866.23 ± 5.48, 215.82 ± 2.16, 1979.48 ± 11.47 and 204.50 ± 1.10 μA/mM for Hg(II), Cu(II), Pb(II) and Cd(II), respectively. The selectivity of the clicked-CoPc modified GCE toward Hg(II), Cu(II), Pb(II), Cd(II) present no interference from these metals ions. The fabricated electrochemical sensor exhibited very good electrochemical properties such as good reproducibility, stability, reusability and is suitable for the detection of heavy metal ions in tap water in our laboratory.
- Full Text:
- Date Issued: 2018
- Authors: Fomo, Gertrude , Nwaji, Njemuwa , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187914 , vital:44709 , xlink:href="https://doi.org/10.1016/j.jelechem.2018.02.016"
- Description: Beside different methods and materials used to develop electrochemical sensors, the modification of the electrode using click reaction based on metallophthalocyanine (MPc) compounds are shown to improve the stability and sensitivity of the sensor. This work reported the development of electrochemical sensor for mercury (II), Lead (II), copper (II) and cadmium (II) ions detection based on the synthesized novel low symmetry alkyne terminated cobalt Phthalocyanine (CoPc) derivative. Differential pulse stripping voltammetry (DPSV) technique was employed for the first time in simultaneous determination of trace levels of the above metal ions using modified glassy carbon electrode (GCE) via click chemistry. Under the optimum experimental conditions, the anodic peak current is proportional to the concentrations of metal ions over a wide range of 0 to 0.1 mM with nanolevel detection limit of 81.94, 327.71, 55.87 and 347.06 nM and the sensitivity of 866.23 ± 5.48, 215.82 ± 2.16, 1979.48 ± 11.47 and 204.50 ± 1.10 μA/mM for Hg(II), Cu(II), Pb(II) and Cd(II), respectively. The selectivity of the clicked-CoPc modified GCE toward Hg(II), Cu(II), Pb(II), Cd(II) present no interference from these metals ions. The fabricated electrochemical sensor exhibited very good electrochemical properties such as good reproducibility, stability, reusability and is suitable for the detection of heavy metal ions in tap water in our laboratory.
- Full Text:
- Date Issued: 2018
Unquenched fluorescence lifetime for β-phenylthio substituted zinc phthalocyanine upon conjugation to gold nanoparticles
- Forteath, Shaun, Antunes, Edith M, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245774 , vital:51404 , xlink:href="https://doi.org/10.1016/j.poly.2011.12.015"
- Description: Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh)4). The conjugates formed are represented as ZnPc(SPh)4–AuNP. The absorption spectrum of the ZnPc(SPh)4–AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).
- Full Text:
- Date Issued: 2012
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245774 , vital:51404 , xlink:href="https://doi.org/10.1016/j.poly.2011.12.015"
- Description: Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh)4). The conjugates formed are represented as ZnPc(SPh)4–AuNP. The absorption spectrum of the ZnPc(SPh)4–AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).
- Full Text:
- Date Issued: 2012
Synthesis and photophysical behavior of a novel zinc phthalocyanine containing a single carboxylic acid and three phenylthio substituents
- Forteath, Shaun, Antunes, Edith M, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243207 , vital:51127 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.03.050"
- Description: Zinc 2, (3)-tri-(phenylthio)-2, (3)-carboxy phthalocyanine (ZnPc(COOH)(SPh)3), zinc 2, (3)-tetra-(phenylthio) phthalocyanine (ZnPc(SPh)4) and 2, (3)-tetra-(phenylthio) phthalocyanine (H2Pc(SPh)4) were synthesized and their photophysical behavior were compared with those of a number of zinc phthalocyanine (ZnPc) derivatives. ZnPc(COOH)(SPh)3 and ZnPc(SPh)4 had similar fluorescence (ΦF=0.14) and triplet state (ΦT=0.65) quantum yields in dimethylsulfoxide, hence showing no effects of the replacement of one of the phenylthio groups with a carboxylic acid group. ZnPc(COOH)(SPh)3 displayed a slightly shorter triplet lifetime (τT=331 μs) than ZnPc (τT=350 μs) in DMSO, but within the range of ZnPc derivatives. The triplet lifetime for ZnPc(COOH)(SPh)3 is much longer than for the symmetrical derivative (ZnPc(SPh)4) with τT=149 μs in DMSO.
- Full Text:
- Date Issued: 2012
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243207 , vital:51127 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.03.050"
- Description: Zinc 2, (3)-tri-(phenylthio)-2, (3)-carboxy phthalocyanine (ZnPc(COOH)(SPh)3), zinc 2, (3)-tetra-(phenylthio) phthalocyanine (ZnPc(SPh)4) and 2, (3)-tetra-(phenylthio) phthalocyanine (H2Pc(SPh)4) were synthesized and their photophysical behavior were compared with those of a number of zinc phthalocyanine (ZnPc) derivatives. ZnPc(COOH)(SPh)3 and ZnPc(SPh)4 had similar fluorescence (ΦF=0.14) and triplet state (ΦT=0.65) quantum yields in dimethylsulfoxide, hence showing no effects of the replacement of one of the phenylthio groups with a carboxylic acid group. ZnPc(COOH)(SPh)3 displayed a slightly shorter triplet lifetime (τT=331 μs) than ZnPc (τT=350 μs) in DMSO, but within the range of ZnPc derivatives. The triplet lifetime for ZnPc(COOH)(SPh)3 is much longer than for the symmetrical derivative (ZnPc(SPh)4) with τT=149 μs in DMSO.
- Full Text:
- Date Issued: 2012
Borneol-triarylcorrole hybrids with chiral-optical response and anticancer behaviours
- Fu, Bo, Wang, Lin, Yu, Xiaoxiao, Fang, Xianying, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Liang, Xu, Xu, Haijun
- Authors: Fu, Bo , Wang, Lin , Yu, Xiaoxiao , Fang, Xianying , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu , Xu, Haijun
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185294 , vital:44362 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109699"
- Description: A series of four multifunctional A2B type H3corroles with meso-borneol substituents at the B position have been synthesized and characterized. A detailed analysis of the optical properties was carried out, and a comparison was made with theoretical calculations to identify the key trends in the structure-property relationships. The meso-borneol substituent couples with the corrole core leading to clear CD signals in the B band region. Enhanced anti-cancer properties are observed in vitro relative to (−)-borneol with cell inhibition rates of up to 94%.
- Full Text:
- Date Issued: 2021
- Authors: Fu, Bo , Wang, Lin , Yu, Xiaoxiao , Fang, Xianying , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu , Xu, Haijun
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185294 , vital:44362 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109699"
- Description: A series of four multifunctional A2B type H3corroles with meso-borneol substituents at the B position have been synthesized and characterized. A detailed analysis of the optical properties was carried out, and a comparison was made with theoretical calculations to identify the key trends in the structure-property relationships. The meso-borneol substituent couples with the corrole core leading to clear CD signals in the B band region. Enhanced anti-cancer properties are observed in vitro relative to (−)-borneol with cell inhibition rates of up to 94%.
- Full Text:
- Date Issued: 2021
Organosilicon compounds as fluorescent chemosensors for fluoride anion recognition
- Gai, Lizhi, Mack, John, Lu, Hua, Nyokong, Tebello, Li, Zhifang, Kobayashi, Nagao, Shen, Zhen
- Authors: Gai, Lizhi , Mack, John , Lu, Hua , Nyokong, Tebello , Li, Zhifang , Kobayashi, Nagao , Shen, Zhen
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241424 , vital:50938 , xlink:href="https://doi.org/10.1016/j.ccr.2014.10.009"
- Description: Recent developments in organosilicon-based chemosensors for F− recognition are reviewed. The design strategies for improving the photophysical properties of organosilicon-based chemosensors are elaborated, with an emphasis placed on their utility for biological applications. The photophysical properties and electronic structures are analyzed in depth with reference made to the results of molecular modeling calculation and possible future research directions are assessed.
- Full Text:
- Date Issued: 2015
- Authors: Gai, Lizhi , Mack, John , Lu, Hua , Nyokong, Tebello , Li, Zhifang , Kobayashi, Nagao , Shen, Zhen
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241424 , vital:50938 , xlink:href="https://doi.org/10.1016/j.ccr.2014.10.009"
- Description: Recent developments in organosilicon-based chemosensors for F− recognition are reviewed. The design strategies for improving the photophysical properties of organosilicon-based chemosensors are elaborated, with an emphasis placed on their utility for biological applications. The photophysical properties and electronic structures are analyzed in depth with reference made to the results of molecular modeling calculation and possible future research directions are assessed.
- Full Text:
- Date Issued: 2015
Synthesis and pharmacological evaluation of chlorin derivatives for photodynamic therapy of cholangiocarcinoma
- Gao, Ying-Hua, Li, Man-Yi, Saijad, Faiza, Wang, Jin-Hai, Meharban, Faiza, Gadoora, Malaz A, Yan, Yi-Jia, Nyokong, Tebello, Chen, Zhi-Long
- Authors: Gao, Ying-Hua , Li, Man-Yi , Saijad, Faiza , Wang, Jin-Hai , Meharban, Faiza , Gadoora, Malaz A , Yan, Yi-Jia , Nyokong, Tebello , Chen, Zhi-Long
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190873 , vital:45036 , xlink:href="https://doi.org/10.1016/j.ejmech.2020.112049"
- Description: Photodynamic therapy (PDT) has been developed as a promising therapeutic method in cancer treatment. The discovery of effective photosensitizer, which is the key factor of PDT, is highly desired. This paper reports the synthesis of novel chlorin derivatives, 5,10,15,20-tetraphenyl-[2:3]-[(methoxycarbonyl, carboxy)methano] chlorin I and 5,10,15,20-tetraphenyl-[2:3]- {[methoxycarbonyl, (2-hydroxyethyl)amide]methano}chlorin II. Their structures were characterized with UV–vis, 1HNMR, 13CNMR and HRMS spectroscopies. Photophysical and photochemical experiments results showed that compound I and II had an absorption maximum around 650 nm, with molar extinction coefficients of 1 × 104 M−1 cm−1. They had strong fluorescence emission in 650–660 nm upon excitation with 419–422 nm light. ESR showed that singlet oxygen was produced upon irradiation of compounds with 650 nm light in the presence of molecular oxygen. The photo-bleaching test indicated that the structure of compounds was stable. These new compounds exhibit excellent anti-tumor effects and lower toxicity compared to m-THPC in vitro and in vivo. Compound I and II had high tumor selectivity, which could induced tumor cells shrinkage and necrosis under 650 nm laser irradiation. Flow cytometry revealed that the compounds might mediate PDT effect at late apoptotic phase. These results make these compound I and II promising candidates for future study in photo-diagnosis and photodynamic therapy of cholangiocarcinoma.
- Full Text:
- Date Issued: 2020
- Authors: Gao, Ying-Hua , Li, Man-Yi , Saijad, Faiza , Wang, Jin-Hai , Meharban, Faiza , Gadoora, Malaz A , Yan, Yi-Jia , Nyokong, Tebello , Chen, Zhi-Long
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190873 , vital:45036 , xlink:href="https://doi.org/10.1016/j.ejmech.2020.112049"
- Description: Photodynamic therapy (PDT) has been developed as a promising therapeutic method in cancer treatment. The discovery of effective photosensitizer, which is the key factor of PDT, is highly desired. This paper reports the synthesis of novel chlorin derivatives, 5,10,15,20-tetraphenyl-[2:3]-[(methoxycarbonyl, carboxy)methano] chlorin I and 5,10,15,20-tetraphenyl-[2:3]- {[methoxycarbonyl, (2-hydroxyethyl)amide]methano}chlorin II. Their structures were characterized with UV–vis, 1HNMR, 13CNMR and HRMS spectroscopies. Photophysical and photochemical experiments results showed that compound I and II had an absorption maximum around 650 nm, with molar extinction coefficients of 1 × 104 M−1 cm−1. They had strong fluorescence emission in 650–660 nm upon excitation with 419–422 nm light. ESR showed that singlet oxygen was produced upon irradiation of compounds with 650 nm light in the presence of molecular oxygen. The photo-bleaching test indicated that the structure of compounds was stable. These new compounds exhibit excellent anti-tumor effects and lower toxicity compared to m-THPC in vitro and in vivo. Compound I and II had high tumor selectivity, which could induced tumor cells shrinkage and necrosis under 650 nm laser irradiation. Flow cytometry revealed that the compounds might mediate PDT effect at late apoptotic phase. These results make these compound I and II promising candidates for future study in photo-diagnosis and photodynamic therapy of cholangiocarcinoma.
- Full Text:
- Date Issued: 2020