Fluorescence Behaviour of an Aluminium Octacarboxy Phthalocyanine-NaYGdF 4
- Taylor, Jessica, Litwinski, Christian, Nyokong, Tebello, Antunes, Edith M
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189503 , vital:44852 , xlink:href="https://doi.org/10.1007/s10895-015-1539-8"
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions).
- Full Text:
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189503 , vital:44852 , xlink:href="https://doi.org/10.1007/s10895-015-1539-8"
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions).
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Synthesis and characterization of Na (Y, Gd) F4 upconversion nanoparticles and an investigation of their effects on the photophysical properties of an unsubstituted tetrathiophenoxy phthalocyanine
- Taylor, Jessica M, Litwinski, Christian, Nyokong, Tebello, Antunes, Edith M
- Authors: Taylor, Jessica M , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241437 , vital:50939 , xlink:href="https://doi.org/10.1007/s11051-015-2889-5"
- Description: Sphere- and star-shaped Na(Y,Gd)F4:Yb/Er(Tm)upconversion nanoparticles (UCNP) were successfully synthesized utilizing a methanol-assisted thermal decomposition approach and their spectroscopic (absorption, emission and luminescence lifetime) properties fully characterized. The factors affecting the size and shape of the UCNPs were studied and discussed in detail. The size of the nanoparticles was determined using TEM primarily and found to be approximately 19 and 30 nm for the Er and Tm spheres, respectively, while the Er and Tm “stars” were found to be much larger with sizes ranging from 110 to 240 nm, respectively (as determined along the width of the nanoparticle). In addition, their influence on the spectroscopic properties of an unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) was investigated. The UCNP were found to produce characteristic upconversion luminescence emissions in the blue, green, red and NIR regions. Simple mixing with an H2Pc in toluene was found to exert no obvious changes in the spectroscopic properties of the Pc, although a considerable increase in the radiative lifetimes is observed for the Pc in the presence of the UCNPs. The singlet oxygen generation mediated by the red light excitation of the H2Pc mixed with UCNP was found to decrease in the presence of the NPs.
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- Authors: Taylor, Jessica M , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241437 , vital:50939 , xlink:href="https://doi.org/10.1007/s11051-015-2889-5"
- Description: Sphere- and star-shaped Na(Y,Gd)F4:Yb/Er(Tm)upconversion nanoparticles (UCNP) were successfully synthesized utilizing a methanol-assisted thermal decomposition approach and their spectroscopic (absorption, emission and luminescence lifetime) properties fully characterized. The factors affecting the size and shape of the UCNPs were studied and discussed in detail. The size of the nanoparticles was determined using TEM primarily and found to be approximately 19 and 30 nm for the Er and Tm spheres, respectively, while the Er and Tm “stars” were found to be much larger with sizes ranging from 110 to 240 nm, respectively (as determined along the width of the nanoparticle). In addition, their influence on the spectroscopic properties of an unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) was investigated. The UCNP were found to produce characteristic upconversion luminescence emissions in the blue, green, red and NIR regions. Simple mixing with an H2Pc in toluene was found to exert no obvious changes in the spectroscopic properties of the Pc, although a considerable increase in the radiative lifetimes is observed for the Pc in the presence of the UCNPs. The singlet oxygen generation mediated by the red light excitation of the H2Pc mixed with UCNP was found to decrease in the presence of the NPs.
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Catalytic oxidation of thioanisole using oxovanadium (IV)‐functionalized electrospun polybenzimidazole nanofibers
- Walmsley, Ryan S, Hlangothi, Percy, Litwinski, Christian, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Walmsley, Ryan S , Hlangothi, Percy , Litwinski, Christian , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242083 , vital:51000 , xlink:href="https://doi.org/10.1002/app.38067"
- Description: Polybenzimidazole fibers, with an average diameter of 262 nm, were produced by the process of electrospinning. These fibers were used as a solid support material for the immobilization of oxovanadium(IV) which was achieved via a reaction with vanadyl sulfate. The oxovanadium(IV)-functionalized nanofibers were used as heterogeneous catalysts for the oxidation of thioanisole under both batch and pseudo-continuous flow conditions with great success. Under batch conditions near quantitative oxidation of thioanisole was achieved in under 90 min, even after four successive catalytic reactions. Under continuous conditions, excellent conversion of thioanisole was maintained throughout the period studied at flow rates of up to 2 mLh−1. This study, therefore, proposes that electrospun polybenzimidazole nanofibers, with their small diameters, impressive chemical and thermal stability, as well as coordinating benzimidazole group, may be a desirable support material for immobilization of homogeneous catalysts.
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- Authors: Walmsley, Ryan S , Hlangothi, Percy , Litwinski, Christian , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242083 , vital:51000 , xlink:href="https://doi.org/10.1002/app.38067"
- Description: Polybenzimidazole fibers, with an average diameter of 262 nm, were produced by the process of electrospinning. These fibers were used as a solid support material for the immobilization of oxovanadium(IV) which was achieved via a reaction with vanadyl sulfate. The oxovanadium(IV)-functionalized nanofibers were used as heterogeneous catalysts for the oxidation of thioanisole under both batch and pseudo-continuous flow conditions with great success. Under batch conditions near quantitative oxidation of thioanisole was achieved in under 90 min, even after four successive catalytic reactions. Under continuous conditions, excellent conversion of thioanisole was maintained throughout the period studied at flow rates of up to 2 mLh−1. This study, therefore, proposes that electrospun polybenzimidazole nanofibers, with their small diameters, impressive chemical and thermal stability, as well as coordinating benzimidazole group, may be a desirable support material for immobilization of homogeneous catalysts.
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Optical limiting analysis of phthalocyanines in polymer thin films
- Britton, Jonathan, Litwinski, Christian, Antunes, Edith M, Durmus, Mahmut, Chaukea, Vongani, Nyokong, Tebello
- Authors: Britton, Jonathan , Litwinski, Christian , Antunes, Edith M , Durmus, Mahmut , Chaukea, Vongani , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232488 , vital:49996 , xlink:href="https://doi.org/10.1080/10601325.2013.736269"
- Description: This paper reports on the effect of embedding twelve phthalocyanines containing In, Ga, Zn and Al as central metals in polymer thin films on their optical limiting abilities. This paper also examines the effect of forming a covalent link between zinc tetraamino phthalocyanine (10) and poly (methyl acrylic acid) (PMAA), and Zn (11) or OHAl (12) octacarboxy phthalocyanines with polyethylenimine (PEI). The average film thickness (for phthalocyanines mixed or linked to polymers) of each Pc/Polymer films on glass was 95 μm. The hyperpolarizability of the twelve phthalocyanines was found to be in the range of 10−26 to 10−24 esu.L. This is significantly higher than the hyperpolarizabilities of these phthalocyanines in solution, which ranged from 10−30 to 10−26 esu.L. Degradation studies seem to indicate that placing a phthalocyanine within a polymer thin film may protect it slightly from photo- and thermal degradation.
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- Authors: Britton, Jonathan , Litwinski, Christian , Antunes, Edith M , Durmus, Mahmut , Chaukea, Vongani , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232488 , vital:49996 , xlink:href="https://doi.org/10.1080/10601325.2013.736269"
- Description: This paper reports on the effect of embedding twelve phthalocyanines containing In, Ga, Zn and Al as central metals in polymer thin films on their optical limiting abilities. This paper also examines the effect of forming a covalent link between zinc tetraamino phthalocyanine (10) and poly (methyl acrylic acid) (PMAA), and Zn (11) or OHAl (12) octacarboxy phthalocyanines with polyethylenimine (PEI). The average film thickness (for phthalocyanines mixed or linked to polymers) of each Pc/Polymer films on glass was 95 μm. The hyperpolarizability of the twelve phthalocyanines was found to be in the range of 10−26 to 10−24 esu.L. This is significantly higher than the hyperpolarizabilities of these phthalocyanines in solution, which ranged from 10−30 to 10−26 esu.L. Degradation studies seem to indicate that placing a phthalocyanine within a polymer thin film may protect it slightly from photo- and thermal degradation.
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Oxovanadium (IV)-containing poly (styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) electrospun nanofibers for the catalytic oxidation of thioanisole
- Walmsley, Ryan S, Litwinski, Christian, Antunes, Edith M, Hlangothi, Percy, Hosten, Eric C, McCleland, Cedric, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Walmsley, Ryan S , Litwinski, Christian , Antunes, Edith M , Hlangothi, Percy , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241665 , vital:50959 , xlink:href="https://doi.org/10.1016/j.molcata.2013.07.018"
- Description: The catalytic fibers have been fabricated by the electrospinning of a copolymer of styrene and 2-(2′-hydroxy-4′-ethenylphenyl)imidazole {p(ST-co-VPIM)} followed by a reaction with a methanolic vanadyl solution to afford the oxovanadium(IV)-containing poly(styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) fibers {p(ST-co-VPIM)-VO fibers}. The relationship between polymer concentration and fiber diameter was investigated, and at high concentration (20 wt%) the fibers were quite large (average diameter of 3.8 μm) but as the concentration was reduced fibers of much lower diameter were produced (0.6 μm using 8 wt%). The BET surface area for p(ST-co-VPIM) fibers (0.6 μm diameter) was 47.9 m2 g−1 and functionalization of p(ST-co-VPIM) with vanadyl resulted in an increase in surface area to 60.7 m2 g−1 for p(ST-co-VPIM)-VO. The presence of vanadyl was confirmed by XPS and EPR. The EPR spectral analyses depicted complex speciation of vanadium within these polymer supports. These catalytic fibers were applied under batch and continuous flow conditions for the catalytic oxidation of thioanisole using hydrogen peroxide. The continuous flow method gave excellent and constant conversion throughout the 10 h period studied. The leaching of vanadium from the fiber support was 4% over the 10 h period indicating a significant stability of the material.
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- Authors: Walmsley, Ryan S , Litwinski, Christian , Antunes, Edith M , Hlangothi, Percy , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241665 , vital:50959 , xlink:href="https://doi.org/10.1016/j.molcata.2013.07.018"
- Description: The catalytic fibers have been fabricated by the electrospinning of a copolymer of styrene and 2-(2′-hydroxy-4′-ethenylphenyl)imidazole {p(ST-co-VPIM)} followed by a reaction with a methanolic vanadyl solution to afford the oxovanadium(IV)-containing poly(styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) fibers {p(ST-co-VPIM)-VO fibers}. The relationship between polymer concentration and fiber diameter was investigated, and at high concentration (20 wt%) the fibers were quite large (average diameter of 3.8 μm) but as the concentration was reduced fibers of much lower diameter were produced (0.6 μm using 8 wt%). The BET surface area for p(ST-co-VPIM) fibers (0.6 μm diameter) was 47.9 m2 g−1 and functionalization of p(ST-co-VPIM) with vanadyl resulted in an increase in surface area to 60.7 m2 g−1 for p(ST-co-VPIM)-VO. The presence of vanadyl was confirmed by XPS and EPR. The EPR spectral analyses depicted complex speciation of vanadium within these polymer supports. These catalytic fibers were applied under batch and continuous flow conditions for the catalytic oxidation of thioanisole using hydrogen peroxide. The continuous flow method gave excellent and constant conversion throughout the 10 h period studied. The leaching of vanadium from the fiber support was 4% over the 10 h period indicating a significant stability of the material.
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The synthesis and characterisation of magnetic nanoparticles and their interaction with a zinc phthalocyanine
- Antunes, Edith M, Rapulenyane, Nomasonto, Ledwaba, Mpho, Litwinski, Christian, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Antunes, Edith M , Rapulenyane, Nomasonto , Ledwaba, Mpho , Litwinski, Christian , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242111 , vital:51002 , xlink:href="https://doi.org/10.1016/j.inoche.2012.12.010"
- Description: A variety of nanoparticles (NPs), including FePt nanoparticles with Fe as the shell (2) or Pt as the shell (3), Pt NPs (4), and FePd (5) were synthesised, characterised and their effect on a zinc phthalocyanine (1) tetra-substituted with a pyridyl-oxy substituent studied using UV/Vis and fluorescence spectroscopy (including time correlated single photon counting, TCSPC). The nanoparticles were characterised using a number of techniques including UV/Vis and inductively coupled plasma-optical emission (ICP-OES) spectroscopies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and electron paramagnetic resonance (EPR) spectroscopy. Nanocomposites (NCs, 6,7) where the ZnPc (1) was used as the stabiliser, instead of oleic acid and or oleylamine, were also synthesised and characterised.
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- Authors: Antunes, Edith M , Rapulenyane, Nomasonto , Ledwaba, Mpho , Litwinski, Christian , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242111 , vital:51002 , xlink:href="https://doi.org/10.1016/j.inoche.2012.12.010"
- Description: A variety of nanoparticles (NPs), including FePt nanoparticles with Fe as the shell (2) or Pt as the shell (3), Pt NPs (4), and FePd (5) were synthesised, characterised and their effect on a zinc phthalocyanine (1) tetra-substituted with a pyridyl-oxy substituent studied using UV/Vis and fluorescence spectroscopy (including time correlated single photon counting, TCSPC). The nanoparticles were characterised using a number of techniques including UV/Vis and inductively coupled plasma-optical emission (ICP-OES) spectroscopies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and electron paramagnetic resonance (EPR) spectroscopy. Nanocomposites (NCs, 6,7) where the ZnPc (1) was used as the stabiliser, instead of oleic acid and or oleylamine, were also synthesised and characterised.
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Ultrafast Photodynamics of the Indoline Dye D149 Adsorbed to Porous ZnO in Dye‐Sensitized Solar Cells
- Rohwer, Egmont, Richter, Christoph, Heming, Nadine, Strauch, Kerstin, Litwinski, Christian, Nyokong, Tebello, Schlettwein, Derck, Schwoerer, Heinrich
- Authors: Rohwer, Egmont , Richter, Christoph , Heming, Nadine , Strauch, Kerstin , Litwinski, Christian , Nyokong, Tebello , Schlettwein, Derck , Schwoerer, Heinrich
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242153 , vital:51006 , xlink:href="https://doi.org/10.1002/cphc.201200715"
- Description: We investigate the ultrafast dynamics of the photoinduced electron transfer between surface-adsorbed indoline D149 dye and porous ZnO as used in the working electrodes of dye-sensitized solar cells. Transient absorption spectroscopy was conducted on the dye in solution, on solid state samples and for the latter in contact to a I−/I3− redox electrolyte typical for dye-sensitized solar cells to elucidate the effect of each component in the observed dynamics. D149 in a solution of 1:1 acetonitrile and tert-butyl alcohol shows excited-state lifetimes of 300±50 ps. This signature is severely quenched when D149 is adsorbed to ZnO, with the fastest component of the decay trace measured at 150±20 fs due to the charge-transfer mechanism. Absorption bands of the oxidized dye molecule were investigated to determine regeneration times which are in excess of 1 ns. The addition of the redox electrolyte to the system results in faster regeneration times, of the order of 1 ns.
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- Authors: Rohwer, Egmont , Richter, Christoph , Heming, Nadine , Strauch, Kerstin , Litwinski, Christian , Nyokong, Tebello , Schlettwein, Derck , Schwoerer, Heinrich
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242153 , vital:51006 , xlink:href="https://doi.org/10.1002/cphc.201200715"
- Description: We investigate the ultrafast dynamics of the photoinduced electron transfer between surface-adsorbed indoline D149 dye and porous ZnO as used in the working electrodes of dye-sensitized solar cells. Transient absorption spectroscopy was conducted on the dye in solution, on solid state samples and for the latter in contact to a I−/I3− redox electrolyte typical for dye-sensitized solar cells to elucidate the effect of each component in the observed dynamics. D149 in a solution of 1:1 acetonitrile and tert-butyl alcohol shows excited-state lifetimes of 300±50 ps. This signature is severely quenched when D149 is adsorbed to ZnO, with the fastest component of the decay trace measured at 150±20 fs due to the charge-transfer mechanism. Absorption bands of the oxidized dye molecule were investigated to determine regeneration times which are in excess of 1 ns. The addition of the redox electrolyte to the system results in faster regeneration times, of the order of 1 ns.
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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%.
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- 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%.
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Tetra and octa (2, 6-di-iso-propylphenoxy)-substituted phthalocyanines
- Tuhl, Ahmad, Chidawanayika, Wadzanai J U, Ibrahim, Hamada Mohamed, Al-Awadi, Nouria, Litwinski, Christian, Nyokong, Tebello, Behbehani, Haider, Manaa, Hacene, Makhseed, Saad
- Authors: Tuhl, Ahmad , Chidawanayika, Wadzanai J U , Ibrahim, Hamada Mohamed , Al-Awadi, Nouria , Litwinski, Christian , Nyokong, Tebello , Behbehani, Haider , Manaa, Hacene , Makhseed, Saad
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245855 , vital:51411 , xlink:href="https://doi.org/10.1142/S1088424612004495"
- Description: This work reports on the synthesis of novel metal free, zinc, aluminum, gallium and indium tetra and octa (2,6-di-iso-propylphenoxy)-substituted phthalocyanine derivatives. UV-visible and 1H NMR analyses confirm that a non-planar conformation, adapted by the phenoxy substituents due to steric interaction in both derivative series, perfectly discourage cofacial aggregation. Fluorescence quantum yields vary as a function of the number of substituents on the ring periphery, while the fluorescence lifetimes display no distinct trend. Triplet quantum yields are significantly larger for the tetra 2,6-di-iso-propylphenoxy- substituted derivatives relative to their corresponding octa-substituted species. However there was no overall trend in the triplet lifetime values. For almost all of the phthalocyanine derivatives, singlet oxygen was produced with relatively good quantum yields. This study explores the possibility of fine-tuning their physicochemical properties by simple structural modification.
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- Authors: Tuhl, Ahmad , Chidawanayika, Wadzanai J U , Ibrahim, Hamada Mohamed , Al-Awadi, Nouria , Litwinski, Christian , Nyokong, Tebello , Behbehani, Haider , Manaa, Hacene , Makhseed, Saad
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245855 , vital:51411 , xlink:href="https://doi.org/10.1142/S1088424612004495"
- Description: This work reports on the synthesis of novel metal free, zinc, aluminum, gallium and indium tetra and octa (2,6-di-iso-propylphenoxy)-substituted phthalocyanine derivatives. UV-visible and 1H NMR analyses confirm that a non-planar conformation, adapted by the phenoxy substituents due to steric interaction in both derivative series, perfectly discourage cofacial aggregation. Fluorescence quantum yields vary as a function of the number of substituents on the ring periphery, while the fluorescence lifetimes display no distinct trend. Triplet quantum yields are significantly larger for the tetra 2,6-di-iso-propylphenoxy- substituted derivatives relative to their corresponding octa-substituted species. However there was no overall trend in the triplet lifetime values. For almost all of the phthalocyanine derivatives, singlet oxygen was produced with relatively good quantum yields. This study explores the possibility of fine-tuning their physicochemical properties by simple structural modification.
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Optical limiting behavior of ring substituted zinc, indium and gallium phthalocyanines in the presence of quantum dots
- Britton, Jonathan, Litwinski, Christian, Durmus, Mahmut, Chauke, Vongani, Nyokong, Tebello
- Authors: Britton, Jonathan , Litwinski, Christian , Durmus, Mahmut , Chauke, Vongani , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247122 , vital:51548 , xlink:href="https://doi.org/10.1142/S1088424611004142"
- Description: This paper presents the study of the effects of CdTe-TGA quantum dots (QDs) on optical limiting ability of different phthalocyanine (Pc) complexes (1–10) containing Zn, Ga, In central metals and substituted with benzyloxyphenoxy, phenoxy, tert-butylphenoxy and amino groups. The optical limiting parameters of Pcs were higher for tert-butylphenoxy when compared to benzyloxyphenoxy and phenoxy substituents, in DMSO. Non-peripheral substitution decreased the optical limiting parameters. Third-order susceptibility (Im[χ(3)]/α) values of Pcs in the absence and presence of CdTe QDs were in the 10-12 to 10-10 esu.cm range. Hyperpolarizabilities (γ) ranged from 10-31 to 10-29 esu L for Pc alone or in mixture with QDs. There is a general improvement in optical limiting ability of Pc complexes in the presence of CdTe TGA QDs. Due to these promising results, future work can be implemented for the creation of Pc:QD thin films, which would then be examined to ensure that their optical limiting ability is still acceptable.
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- Authors: Britton, Jonathan , Litwinski, Christian , Durmus, Mahmut , Chauke, Vongani , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247122 , vital:51548 , xlink:href="https://doi.org/10.1142/S1088424611004142"
- Description: This paper presents the study of the effects of CdTe-TGA quantum dots (QDs) on optical limiting ability of different phthalocyanine (Pc) complexes (1–10) containing Zn, Ga, In central metals and substituted with benzyloxyphenoxy, phenoxy, tert-butylphenoxy and amino groups. The optical limiting parameters of Pcs were higher for tert-butylphenoxy when compared to benzyloxyphenoxy and phenoxy substituents, in DMSO. Non-peripheral substitution decreased the optical limiting parameters. Third-order susceptibility (Im[χ(3)]/α) values of Pcs in the absence and presence of CdTe QDs were in the 10-12 to 10-10 esu.cm range. Hyperpolarizabilities (γ) ranged from 10-31 to 10-29 esu L for Pc alone or in mixture with QDs. There is a general improvement in optical limiting ability of Pc complexes in the presence of CdTe TGA QDs. Due to these promising results, future work can be implemented for the creation of Pc:QD thin films, which would then be examined to ensure that their optical limiting ability is still acceptable.
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Photophysical and photochemical behavior of electrospun fibers of a polyurethane polymer chemically linked to lutetium carboxyphenoxy phthalocyanine
- Zugle, Ruphino, Litwinski, Christian, Torto, Nelson, Nyokong, Tebello
- Authors: Zugle, Ruphino , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248428 , vital:51685 , xlink:href="https://doi.org/10.1039/C1NJ20126C"
- Description: A phthalocyanine complex of lutetium substituted with four peripherally substituted 4-carboxyphenoxy groups was synthesized using cyclotetramerisation reaction. Its structure was elucidated using conventional spectroscopic methods and elemental analysis. The spectral behavior of the complex was studied in DMF solution and in a solid polyurethane fiber matrix. The UV-Visible spectrum showed a red shift in its Q-band maximum absorption within the fiber as compared to that in solution. The triplet quantum yield in DMF was determined to be 0.51 with a lifetime of 2.7 μs and a singlet oxygen quantum yield of 0.33 with a lifetime of 19.85 μs in the same solvent. The functionalized phthalocyanine fiber could be a promising fabric material for applications such as self-disinfecting in wound dressing. A method based on the conversion of ADMA was used to estimate the singlet oxygen quantum yield of the Pc in the hybrid fiber. An estimated singlet oxygen quantum yield value of 0.11 in aqueous medium was obtained. The fluorescence quantum yield of the Pc was found to be 0.01 with a lifetime of 3.20 ns in DMF.
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- Authors: Zugle, Ruphino , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248428 , vital:51685 , xlink:href="https://doi.org/10.1039/C1NJ20126C"
- Description: A phthalocyanine complex of lutetium substituted with four peripherally substituted 4-carboxyphenoxy groups was synthesized using cyclotetramerisation reaction. Its structure was elucidated using conventional spectroscopic methods and elemental analysis. The spectral behavior of the complex was studied in DMF solution and in a solid polyurethane fiber matrix. The UV-Visible spectrum showed a red shift in its Q-band maximum absorption within the fiber as compared to that in solution. The triplet quantum yield in DMF was determined to be 0.51 with a lifetime of 2.7 μs and a singlet oxygen quantum yield of 0.33 with a lifetime of 19.85 μs in the same solvent. The functionalized phthalocyanine fiber could be a promising fabric material for applications such as self-disinfecting in wound dressing. A method based on the conversion of ADMA was used to estimate the singlet oxygen quantum yield of the Pc in the hybrid fiber. An estimated singlet oxygen quantum yield value of 0.11 in aqueous medium was obtained. The fluorescence quantum yield of the Pc was found to be 0.01 with a lifetime of 3.20 ns in DMF.
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Photophysical behavior of zinc monoaminophthalocyanines linked to mercaptopropionic acid-capped CdTe quantum dots
- D'Souza, Sarah, Antunes, Edith M, Litwinski, Christian, Nyokong, Tebello
- Authors: D'Souza, Sarah , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247634 , vital:51602 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.03.005"
- Description: Photosensitizing properties of zinc monoaminophthalocyanine (2) {in the absence or presence of mercaptopropionic acid (MPA) capped CdTe quantum dots (QDs)} were compared with those of mono-aminophenoxy zinc phthalocyanine (3), zinc tetrasulfonated phthalocyanine and zinc phthalocyanine. Complexes 2 and 3 were also linked to the MPA capped CdTe quantum dots through the formation of an amide bond. High triplet state quantum yields were obtained for the linked QD–phthalocyanine derivatives (complexes 2 and 3) compared to when complexes 2 and 3 were mixed with MPA QDs without a chemical bond.
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- Authors: D'Souza, Sarah , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247634 , vital:51602 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.03.005"
- Description: Photosensitizing properties of zinc monoaminophthalocyanine (2) {in the absence or presence of mercaptopropionic acid (MPA) capped CdTe quantum dots (QDs)} were compared with those of mono-aminophenoxy zinc phthalocyanine (3), zinc tetrasulfonated phthalocyanine and zinc phthalocyanine. Complexes 2 and 3 were also linked to the MPA capped CdTe quantum dots through the formation of an amide bond. High triplet state quantum yields were obtained for the linked QD–phthalocyanine derivatives (complexes 2 and 3) compared to when complexes 2 and 3 were mixed with MPA QDs without a chemical bond.
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Photophysical characterization of dysprosium, erbium and lutetium phthalocyanines tetrasubstituted with phenoxy groups at non-peripheral positions
- Zugle, Ruphino, Litwinski, Christian, Nyokong, Tebello
- Authors: Zugle, Ruphino , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247561 , vital:51595 , xlink:href="https://doi.org/10.1016/j.poly.2011.03.030"
- Description: Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01.
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- Authors: Zugle, Ruphino , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247561 , vital:51595 , xlink:href="https://doi.org/10.1016/j.poly.2011.03.030"
- Description: Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01.
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Synthesis and photophysical studies of phthalocyanine–gold nanoparticle conjugates
- Nombona, Nolwazi, Antunes, Edith M, Litwinski, Christian, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248438 , vital:51686 , xlink:href="https://doi.org/10.1039/C1DT11151E"
- Description: This work reports on the synthesis, characterization and photophysical studies of phthalocyanine–gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.
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- Authors: Nombona, Nolwazi , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248438 , vital:51686 , xlink:href="https://doi.org/10.1039/C1DT11151E"
- Description: This work reports on the synthesis, characterization and photophysical studies of phthalocyanine–gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.
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Photophysical properties of newly synthesized fluorinated zinc phthalocyanines in the presence of CdTe quantum dots and the accompanying energy transfer processes
- Erdoğmuş, Ali, Moeno, Sharon, Litwinski, Christian, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Moeno, Sharon , Litwinski, Christian , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262671 , vital:53543 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.014"
- Description: The photophysical properties of two newly synthesized phthalocyanines (Pcs) were studied in the presence and the absence of 3-mercaptopropionic acid (MPA) capped quantum dots (QDs). Energy transfer processes resulting from the combination of QDs and the Pcs: 4-(tetrakis-5-(trifluoromethyl)-2-mercaptopyridinephthalocyaninato)zinc(II) (TtfmMPyZnPc, 3) and 4-(tetrakis-5-(trifluoromethyl)-2-pyridyloxyphthalocyaninato) zinc(II) (TtfmPyZnPc, 4) were also studied. The photophysical properties of the Pcs in the presence of QDs were enhanced and Förster resonance energy transfer (FRET) was observed with the phthalocyanines used. The efficiency of FRET between the QDs and TtfmMPyZnPc and TtfmPyZnPc was found to be 0.31% and 0.45% in DMSO and 0.24% and 0.32% in pyridine, respectively. The triplet state quantum yields for TtfmMPyZnPc and TtfmPyZnPc were found to be 0.86 and 0.74 in DMSO and 0.83 and 0.76 in pyridine.
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- Authors: Erdoğmuş, Ali , Moeno, Sharon , Litwinski, Christian , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262671 , vital:53543 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.014"
- Description: The photophysical properties of two newly synthesized phthalocyanines (Pcs) were studied in the presence and the absence of 3-mercaptopropionic acid (MPA) capped quantum dots (QDs). Energy transfer processes resulting from the combination of QDs and the Pcs: 4-(tetrakis-5-(trifluoromethyl)-2-mercaptopyridinephthalocyaninato)zinc(II) (TtfmMPyZnPc, 3) and 4-(tetrakis-5-(trifluoromethyl)-2-pyridyloxyphthalocyaninato) zinc(II) (TtfmPyZnPc, 4) were also studied. The photophysical properties of the Pcs in the presence of QDs were enhanced and Förster resonance energy transfer (FRET) was observed with the phthalocyanines used. The efficiency of FRET between the QDs and TtfmMPyZnPc and TtfmPyZnPc was found to be 0.31% and 0.45% in DMSO and 0.24% and 0.32% in pyridine, respectively. The triplet state quantum yields for TtfmMPyZnPc and TtfmPyZnPc were found to be 0.86 and 0.74 in DMSO and 0.83 and 0.76 in pyridine.
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Photophysical study of a covalently linked quantum dot–low symmetry phthalocyanine conjugate
- Chidawanyika, Wadzanai J U, Litwinski, Christian, Antunes, Edith M, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
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- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
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