Synthesis and photophysicochemical properties of novel zinc phthalocyanines mono substituted with carboxyl containing functional groups
- Authors: Rapulenyane, Nomasonto , Antunes, Edith M , Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242389 , vital:51037 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.09.007"
- Description: This work reports on the synthesis and the physicochemical properties of novel unsymmetrically substituted zinc phthalocyanines (complexes 8, 10 and 11) and their symmetrically substituted counterparts (complexes 9, 12 and 13). The new complexes and their counterparts were successfully structurally characterized by IR, NMR, mass spectral and elemental analyses. Low fluorescence quantum yields (0.032) and lifetimes (0.91 ns) were obtained for the symmetrical ZnOTPc (complex 9) compared to the higher fluorescence quantum yields (0.15, 0.13, 0.10, 0.09 and 0.29) and lifetimes (4.4, 1.69, 1.69, 2.16 and 3.23 ns) obtained for ZnMPCPc (8), ZnTDTPc (12), ZnMCapPc (10), ZnMCafPc (11) and ZnTCPPc (13), respectively. All the complexes showed the ability to produce singlet oxygen with the highest triplet quantum yields obtained for 8 and 10 (0.80 and 0.65 respectively). High triplet lifetimes (109–286 μs) were obtained for all complexes. Complex 8 showed the longest triplet and fluorescence lifetimes as well the largest triplet state and singlet oxygen quantum yields.
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- Date Issued: 2012
Comparative behavior of conjugates of tantalum phthalocyanines with gold nanoparticles or single walled carbon nanotubes towards bisphenol A electrocatalysis
- Authors: Chauke, Vongani P , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247152 , vital:51551 , xlink:href="https://doi.org/10.1016/j.jelechem.2011.06.019"
- Description: The characterization of tantalum phthalocyanine conjugates with gold nanoparticles and single wall carbon nanotubes as well as their electrocatalytic oxidation of bisphenol A is hereby presented. The formation of the conjugates was confirmed by X-ray diffraction and transmission electron microscope techniques. Single walled carbon nanotube conjugates of TaPc complexes showed the best catalysis as well as less passivation for bisphenol A detection and significant recovery of ∼98% compared to gold nanoparticle conjugates.
- Full Text:
- Date Issued: 2011
Cyclic voltammetry and spectroelectrochemistry of a novel manganese phthalocyanine substituted with hexynyl groups
- Authors: Quinton, Damien , Antunes, Edith M , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248450 , vital:51687 , xlink:href="https://doi.org/10.1016/j.inoche.2010.11.029"
- Description: We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine (3), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).
- Full Text:
- Date Issued: 2011
Investigation of homogeneous photosensitized oxidation activities of palladium and platinum octasubstituted phthalocyanines
- Authors: Ogunbayo, Taofeek B , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248394 , vital:51682 , xlink:href="https://doi.org/10.1016/j.molcata.2010.11.008"
- Description: Photosensitized oxidation of 4-nitrophenol was studied in organic solutions with seven octasubstituted thio and aryloxy palladium and platinum phthalocyanines acting as photosensitizers. Kinetic studies conducted also showed that the complexes have different singlet oxygen quenching constants with direct implication on the quantum yield of photodegradation of 4-nitrophenol (Φ4-NP). Palladium analogues gave better results than the platinum analogues in terms of Φ4-NP with palladium-(dodecylthio)phthalocyanine giving the highest yield of 1.8 × 10−3. Gas chromatography (GC) and liquid chromatography connected to a mass spectrometer (LC–MS) were used to confirm the photodegradation products which were hydroquinone and 1,4-benzoquinone.
- Full Text:
- Date Issued: 2011
Synthesis and physicochemical behaviour of aluminium trikis and tetrakis (diaquaplatinum) octacarboxyphthalocynine
- Authors: Malinga, Nduduzo , Dolotova, Olga , Bulgakov, Roman , Antunes, Edith M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242687 , vital:51068 , xlink:href="https://doi.org/10.1016/j.dyepig.2012.05.011"
- Description: The combination of chemotherapy and photodynamic therapy was investigated by the synthesis and characterisation of phthalocyanine conjugates with Pt complexes. The complexes synthesized are: hydroxoaluminum trikis(diaquaplatinum) octacarboxyphthalocyanine (OHAlOCPc(Pt)3) and hydroxoaluminum tetrakis(diaquaplatinum) octacarboxyphthalocyanine (OHAlOCPc(Pt)4). The platinated phthalocyanine complexes gave long triplet lifetimes of 577 and 526 μs for OHAlOCPc(Pt)3 and OHAlOCPc(Pt)4, respectively. The triplet quantum yields were found to be 0.45 for OHAlOCPc(Pt)3 and 0.57 OHAlOCPc(Pt)4 while the singlet oxygen quantum yields were found to be 0.38 and 0.48, respectively.
- Full Text:
- Date Issued: 2012
Electrochemical, spectroscopic and microscopic studies of new manganese phthalocyanine complexes in solution and as self-assembled monolayers on gold
- Authors: Coates, Megan , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261144 , vital:53363 , xlink:href="https://doi.org/10.1142/S1088424610002471"
- Description: Four new manganese(III) phthalocyanines (3a–d), octasubstituted at the peripheral position with pentylthio, decylthio, benzylthio, and phenylthio groups, respectively, were synthesized. Their specific electrochemical, spectroscopic and microscopic properties in solution and as self-assembled monolayers on gold were characterized. The UV-vis spectra confirmed red-shifted Q bands for all the complexes, due to the effect of the central metal and the electron-donating substituents. Three redox couples were visible during cyclic voltammetry studies for the four complexes, and spectroelectrochemistry confirmed the couples as corresponding to MnIIIPc-2/MnIIPc-2 (II) (metal reduction), MnIIPc-2/MnIIPc-3 (III) (ring reduction) and MnIIIPc-1/MnIIIPc-2 (I) (ring oxidation). Electrochemistry was also used to determine the blocking characteristics of the MnPc self-assembled monolayers on gold, which proved to be highly dependent on the type of substituent. Other methods of characterization included Raman spectroscopy, atomic force and scanning electrochemical microscopy analyses of the SAMs.
- Full Text:
- Date Issued: 2010
Photophysical study of a covalently linked quantum dot–low symmetry phthalocyanine conjugate
- 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.
- Full Text:
- Date Issued: 2010
Photooxidation of 4-chlorophenol sensitized by lutetium tetraphenoxy phthalocyanine anchored on electrospun polystyrene polymer fiber
- Authors: Zugle, Ruphino , Antunes, Edith M , Khene, Samson M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245787 , vital:51405 , xlink:href="https://doi.org/10.1016/j.poly.2011.11.005"
- Description: An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.
- Full Text:
- Date Issued: 2012
Nonlinear optical behavior of metal octaphenoxy phthalocyanines
- Authors: Sanusi, Sikiru O , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241717 , vital:50963 , xlink:href="https://doi.org/10.1142/S1088424613500715"
- Description: In this work, we investigated the nonlinear optical absorption properties of chloroaluminum, chlorogallium, chloroindium, zinc and lead octaphenoxy phthalocyanines in a dimethyl sulphoxide solution using 5 ns pulses at 532 nm. Using the Z-scan technique, the nonlinear optical properties and the excited state absorption cross-sections were determined by fitting the Z-scan data. The k value was the highest for Pb derivative at 211, making it the best nonlinear optical material. In terms of hyperpolarizability, Pb derivative (containing a larger central metal) also gave the largest value followed by aluminum derivative (containing a small central metal). The distortion of the ring caused by the central metal is used to explain the hyperpolarizability values. Large nonlinear absorption coefficient values, βeff, in the range of 3.558–4.763 × 10-9 cm.W-1 and low saturation fluence values, Fsat between 21.5–38.5 mJ.cm-2, were obtained for these samples.
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- Date Issued: 2013
The synthesis and fluorescence behaviour of phthalocyanines unsymmetrically substituted with naphthol and carboxy groups
- Authors: Nombona, Nolwazi , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261534 , vital:53418 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.11.010"
- Description: Unsymmetrically substituted phthalocyanines 8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanine, [8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanato]zinc(II), 8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyanine and [8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenoxy)phthalocyanato]zinc(II) were prepared using the mixed phthalonitrile cyclotetramerization of 3-(1-naphthoxy) phthalonitrile with a carboxylic acid phthalonitrile. The phthalocyanines were separated using column chromatography employing a mixture of THF, ammonia and water. The novel compounds were characterized using UV–Vis, IR, 1H NMR and mass spectrometry as well as elemental analysis. Fluorescence quantum yields were found to range from 0.05 to 0.16.
- Full Text:
- Date Issued: 2010
Synthesis and photophysical behavior of axially substituted phthalocyanine, tetrabenzotriazaporphyrin, and triazatetrabenzcorrole phosphorous complexes
- Authors: Antunes, Edith M , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264518 , vital:53741 , xlink:href="https://doi.org/10.1142/S1088424609000048"
- Description: The synthesis of phosphorous phthalocyanines, triazatetrabenzcorroles, and tetrabenzotriazaporphyrins with a variety of axial ligands is reported. The new complexes are: phosphorous dihydroxy tetrabenzotriazaporphyrin (5, PV(OH)2TBTAP), diphenyl phosphorous phthalocyanine (6, [PV(Ph)2Pc](OH)), diphenyl phosphorous triazatetrabenzcorrole (7, PV(Ph)2TBC), and dioctyl phosphorous triazatetrabenzcorrole (8, PV(C8H17)2TBC). The complexes are not aggregated in dimethylsulfoxide (DMSO) and pyridine. Upon axial coordination of a phenyl or octyl group, the complexes are soluble (and not aggregated) in dichloromethane (DCM) and tetrahydrofuran (THF). The triplet lifetimes range from 395 to 546 μs (for complexes 5 to 8), with the P(Ph)2TBC (7) complex showing the longest triplet lifetime (546 μs), while the smallest triplet quantum yield (ΦT = 0.27) was obtained for the [P(Ph)2Pc](OH) (6) complex. [P(OH)2Pc](OH) (3) showed the shortest triplet lifetime (113 μs) and the largest triplet quantum yield (ΦT = 0.52).
- Full Text:
- Date Issued: 2009
The determination of the photosensitizing properties of mercapto substituted phthalocyanine derivatives in the presence of quantum dots capped with mercaptopropionic acid
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247870 , vital:51625 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.12.009"
- Description: This work reports on the synthesis of several novel water soluble metallophthalocyanines containing Zn2+, In3+, Ga3+ or Si4+ as central metal ions and tetra substituted with mercaptoacetic acid and mercaptopropionic acid. The complexes were characterized using infra red, nuclear magnetic resonance and mass spectroscopies as well as elemental analysis. All the complexes are water soluble but the majority are highly aggregated in water and organic solvents. The complex containing Zn as a central metal and mercaptopropionic acid as a substituent was not aggregated allowing for the determination of photophysical parameters. This complex had triplet state quantum yield of 0.61 in DMF and 0.88 in DMSO while the fluorescence quantum yield was 0.13 in DMSO. The determination of photophysical properties of the complex containing Zn as a central metal and mercaptopropionic acid were carried out in the presence of mercaptopropionic acid capped CdTe quantum dots. There is an increase in triplet state quantum yield from 0.88 (for the phthalocyanine alone) to 0.94 (in the presence of CdTe quantum dots) in DMSO.
- Full Text:
- Date Issued: 2011
Synthesis and photophysical properties of a novel zinc photosensitizer and its gold nanoparticle conjugate
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247100 , vital:51546 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.07.007"
- Description: The peripherally tetra substituted zinc phthalocyanine with 1,6-hexanedithiol as substituent (THdTZnPc, 3) was synthesized and is reported for the first time in this work. The potential of this zinc complex as a suitable photosensitizer for use in photodynamic therapy was determined through the investigation of the photophysical and photochemical properties. In this work complex 3 is attached to gold nanoparticles through the terminal thiol groups of the phthalocyanine resulting in a 3-AuNP conjugate whose photophysicochemical properties are investigated. Fluorescence lifetimes were determined using time correlated single photon counting and they show an increase in the abundance of the monomeric species (τ2) for the Pc in the 3-AuNP conjugate: ∼1 and 0.71 (with respective lifetimes 2.69 ns and 2.86 ns) compared to the free complex 3 with abundances of 0.12 and 0.13 (with respective lifetimes 3.36 ns and 3.28 ns) in DMSO and DMF, respectively.
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- Date Issued: 2011
Synthesis of phthalocyanine conjugates with gold nanoparticles and liposomes for photodynamic therapy
- Authors: Nombona, Nolwazi , Maduray, Kaminee , Antunes, Edith M , Karsten, Aletta , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245798 , vital:51406 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2011.11.007"
- Description: The efficiency of [2,9,17,23-tetrakis-(1,6-hexanedithiol)phthalocyaninato]zinc(II) as a photodynamic therapy (PDT) agent was investigated. This compound belongs to the second generation of photosensitizers currently tested for the cellular photo-damage of cancer cells. The production of reactive oxygen species (ROS) and phototoxicity of the photosensitizer were assessed. Healthy fibroblast cells and breast cancer (MCF-7) cells were treated with either free phthalocyanine or phthalocyanine bound to either gold nanoparticles or encapsulated in liposomes. Cell viability studies showed the optimum phototoxic effect on non-malignant cells to be 4.5 J cm−2. The PDT effect of the liposome bound phthalocyanine showed extensive damage of the breast cancer cells. Gold nanoparticles only showed a modest improvement in PDT activity.
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- Date Issued: 2012
The identification of the UV degradants of melatonin and their ability to scavenge free radicals
- Authors: Maharaj, Deepa S , Anoopkumar-Dukie, Shailendra , Glass, Beverley D , Antunes, Edith M , Lack, Barbara A , Walker, Roderick B , Daya, Santylal
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184303 , vital:44198 , xlink:href="https://doi.org/10.1034/j.1600-079X.2002.01866.x"
- Description: Ultraviolet (UV) light is known to induce the generation of free radicals in biological tissues such as skin. Of these free radicals, the O2–· and particularly the ·OH radical can induce cellular damage including lipid peroxidation. Thus, the use of antioxidants to prevent such damage induced by UV irradiation has received much attention recently. One such antioxidant, which has the potential to be incorporated into sunscreens, is the pineal secretory product melatonin. One of the concerns of using melatonin in sunscreens is its photostability. In the present study, we investigated the photostability of melatonin subjected to UV irradiation. In addition, we used liquid chromatography mass spectrometry (LC-MS) to identify the degradants and we also assessed the ability of the degradants to inhibit O2–· generation as well as lipid peroxidation in rat brain homogenate. The results show that UV irradiation of melatonin (0.1 mg/mL) using a 400-W lamp for 2 hr caused a significant decline of melatonin to 18% of its original concentration after 20 min, with the decline continuing until the melatonin concentration reaches zero at 120 min. The LC-MS results show that the degradants of melatonin are 6-hydroxymelatonin and N1-acetyl-N2-formyl-5-methoxykynurenamine (AFMK). These degradants were able to provide equipotent activity against potassium cyanide (KCN)-induced superoxide generation compared to non-irradiated melatonin. Thus, the study shows that although melatonin is rapidly degraded by UV irradiation, the degradants retain antioxidant activity, making melatonin a likely candidate for inclusion in sunscreens.
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- Date Issued: 2002