Synthesis and characterization of quantum dots designed for biomedical use
- Authors: Kuzyniak, Weronika , Adegoke, Oluwasesan , Sekhosana, Kutloano , D’Souza, Sarah , Tshangana, Sesethu Charmaine , Hoffmann, Björn , Ermilov, Eugeny A. , Nyokong, Tebello , Höpfner, Michael
- Language: English
- Type: Article
- Identifier: vital:7310 , http://hdl.handle.net/10962/d1020387
- Description: Semiconductor quantum dots (QDs) have become promising nanoparticles for a wide variety of biomedical applications. However, the major drawback of QDs is their potential toxicity. Here, we determined possible cytotoxic effects of a set of QDs by systematic photophysical evaluation in vitro as well as in vivo. QDs were synthesized by the hydrothermal aqueous route with sizes in the range of 2.0–3.5 nm. Cytotoxic effects of QDs were studied in the human pancreatic carcinoid cell line BON. Cadmium telluride QDs with or without zinc sulfide shell and coated with 3-mercaptopropionic acid (MPA) were highly cytotoxic even at nanomolar concentrations. Capping with l-glutathione (GSH) or thioglycolic acid (TGA) reduced the cytotoxicity of cadmium telluride QDs and cadmium selenide QDs. Determination of the toxicity of QDs revealed IC50 values in the micromolar range. In vivo studies showed good tolerability of CdSe QDs with ZnS shell and GSH capping. We could demonstrate that QDs with ZnS shell and GSH capping exhibit low toxicity and good tolerability in cell models and living organisms. These QDs appear to be promising candidates for biomedical applications such as drug delivery for enhanced chemotherapy or targeted delivery of light sensitive substances for photodynamic therapy. , Original publication is available at http://dx.doi.org/10.1016/j.ijpharm.2014.03.037
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Synthesis and electrochemical properties of new cobalt and manganese phthalocyanine complexes tetra-substituted with 3,4-(methylendioxy)-phenoxy
- Authors: Erdoğmuş, Ali , Akinbulu, Isaac Adebayo , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7234 , http://hdl.handle.net/10962/d1019672
- Description: The synthesis and electrochemical properties of new cobalt and manganese phthalocyanine complexes, tetra-substituted with 3,4-(methylendioxy)-phenoxy at the peripheral (complexes 3 and 5) and non-peripheral (complexes 4 and 6) positions, are reported. Complexes 3 and 4 showed Q-band absorption, in DMF, at 668 and 686 nm, respectively while Q-band due to complexes 5 and 6 appeared at 732 and 760 nm, respectively in CHCl3. All the complexes showed well resolved redox processes attributed to both metal and ring based processes. Complexes 3 and 4 showed four redox processes, labeled I, II, III and IV. For complex 3, process I (CoIPc−2/CoIPc−3) was observed at −1.45 V, II (CoIIPc−2/CoIPc−2) at −0.38 V, III (CoIIIPc−2/CoIIPc−2) at +0.49 V and IV (CoIIIPc−1/CoIIIPc−2) at +0.97 V versus Ag|AgCl. Similar processes were observed for complex 4 at −1.36 V, −0.27 V, +0.56 V, +1.03 V versus Ag|AgCl, respectively. Complexes 5 and 6 showed two redox processes (I and II). For complex 5, these processes appeared at −0.79 V (MnIIPc−2/MnIIPc−3, I) and −0.07 V versus Ag|AgCl (MnIIIPc−2/MnIIPc−2, II), while for complex 6, they were observed at −0.86 V and −0.04 V versus Ag|AgCl. Spectroelectrochemistry was used to probe and confirm the origin of these processes. , Original publication is availabe at http://dx.doi.org/10.1016/j.poly.2010.05.012
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Synthesis of zinc phthalocyanine derivatives with improved photophysicochemical properties in aqueous media
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7236 , http://hdl.handle.net/10962/d1019687
- Description: The synthesis, photophysical and photochemical properties of new peripherally (β) tetra-substituted thioquinoline Zn(II) (2) and quaternized thioquinoline Zn(II) phthalocyanines (3) and quaternized fluoro functional thiopyridine Zn(II) (5) are described for the first time. These complexes (2, 3 and 5) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. Complexes 2, 4 and 6have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated in all solvents (except for 2 in DMSO) within a wide concentration range. Complexes 3 and 5 showed very good solubility in water as well as DMSO and DMF. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO (2, 4 and 6) and water (3 and 5). Complex 3 gave a very large triplet quantum yield in aqueous media (ΦT = 0.8 in water plus Triton X-100) and a reasonable triplet lifetime of 110 μs. Photophysical and photochemical properties of the phthalocyanines complexes 2–6 are very useful for PDT. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2010.04.048
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Synthesis, characterization and photophysical properties of an acenaphthalene fused-ring-expanded NIR absorbing aza-BODIPY dye
- Authors: Majumdar, Poulomi , Mack, John , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7283 , http://hdl.handle.net/10962/d1020328
- Description: The synthesis and characterization of an NIR absorbing acenaphthalene fused-ring-expanded aza-BODIPY dye are reported. In contrast with its naphtho-fused analogue, a stable complex is obtained when the corresponding phthalonitrile is used as the precursor. A comparison is made with the photophysical properties of 3,5-diphenyl-aza-dibenzoBODIPY. , Original publication is available at http://dx.doi.org/10.1039/C5RA14916A , Arbortext Advanced Print Publisher 9.1.510/W Unicode , Acrobat Distiller 8.1.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
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Synthesis, photophysical and nonlinear optical behavior of neodymium based trisphthalocyanine
- Authors: Sekhosana, Kutloano E , Amuhaya, Edith K , Khene, M Samson , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7243 , http://hdl.handle.net/10962/d1020247
- Description: Tris-{1(4),8(11),15(18),22(25)-tetra(4-tertbutylphenoxy) phthalocyaninato} dineodymium (III) was synthesised and its nonlinear optical and fluorescence behavior was studied. Low fluorescence quantum yield (ФF = 0.03) was obtained with a fluorescence lifetime τF = 4.31 ns for this complex. Nonlinear optical parameters for the complex were determined using the Z-scan technique and the values of Im[χ(3)] and γ were of the order of 10−10 and 10−28 esu, respectively. Square wave voltammetry revealed three reduction and two oxidation couples for the complex. , Original publication is available at http://dx.doi.org/10.1016/j.ica.2014.11.029
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Synthetic pathways to water-soluble phthalocyanines and close analogs
- Authors: Dumoulin, Fabienne , Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7240 , http://hdl.handle.net/10962/d1019720
- Description: The different types of water-soluble phthalocyanines are presented and their synthesis is reviewed. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.002
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The development of catalytic oxovanadium(IV)-containing microspheres for the oxidation of various organosulfur compounds
- Authors: Ogunlaja, Adeniyi S , Khene, M Samson , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Language: English
- Type: Article
- Identifier: vital:7324 , http://hdl.handle.net/10962/d1020574
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil. , Original publication is available at http://dx.doi.org/10.1016/j.apcata.2013.05.004
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The effect of ascorbic acid on the photophysical properties and photodynamic therapy activities of zinc phthalocyanine-single walled carbon nanotube conjugate on MCF-7 cancer cells
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7286 , http://hdl.handle.net/10962/d1020334
- Description: Zinc mono carboxy phenoxy phthalocyanine (1) was chemical modified with ascorbic acid via an ester bond to give ZnMCPPc-AA (2). Complexes 2 and 1 were coordinated to single walled carbon nanotubes via π–π interaction to give ZnMCPPc-AA-SWCNT (3) and ZnMCPPc-SWCNT (4) respectively. Complexes 2, 3 and 4 showed better photophysical properties: with improved triplet lifetimes and quantum yields, and singlet oxygen quantum yields when compared to 1 alone. The photodynamic therapy activities of complexes 1, 2, 3 and 4 were tested in vitro on MCF-7 breast cancer cells. Ascorbic acid suppresses the photodynamic therapy effect of 1, due to its ability to reduce oxidative DNA damage as a result of its potent reducing properties. The highest phototoxicity was observed for 4 which resulted in 77% decrease in cell viability, followed by 3 which resulted in 67% decrease in cell viability. This shows the importance of combination therapy, where the phthalocyanines are the photodynamic therapy agents and single walled carbon nanotubes are the photothermal therapy agents. , Original publication is available at http://dx.doi.org/10.1016/j.saa.2015.06.063
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The effects of gold coated and uncoated zinc oxide nanohexagons on the photophysicochemical properties of the low symmetry zinc phthalocyanine
- Authors: D'Souza, Sarah , Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7280 , http://hdl.handle.net/10962/d1020317
- Description: A new low symmetry, Zn phthalocyanine monosubstituted with diethylaminoethanethiol (mDEAET ZnPc) was synthesized and characterized. This work reports on its photophysical and photochemical properties of mDEAET ZnPc alone and when conjugated to gold coated and uncoated zinc oxide nanohexagons (ZnO NHXs). The photophysicochemical properties generally improved in the presence of the ZnO NHXs. These complexes were also tested for their photodynamic antimicrobial activity against Staphylococcus aureus (S. aureus). The Pc alone showed remarkable growth inhibition even at concentrations as low as 0.05 mg/mL. The conjugates showed a high photoinactivation of S. aureus after 30 min at a fluence of 90 mW cm−2 at a concentration of 0.05 mg/mL. The ZnPc-ZnO NHX conjugates produced the best antimicrobial results. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.06.088
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The nonlinear absorption in new lanthanide double decker pyridine-based phthalocyanines in solution and thin films
- Authors: Sekhosana, Kutloano Edward , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7299 , http://hdl.handle.net/10962/d1020366
- Description: The optical behavior of bis-{2(3), 9(10), 16(17), 23(24)-(tetrapyridin-4-yloxy phthalocyaninato)} lanthanum (III) (2) and its ytterbium (3) counterpart in dimethyl sulfoxide are presented and compared to bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-4-yloxy phthalocyaninato)} ytterbium (III) (4). We report on the third-order susceptibility, second-order hyperpolarizability and the limiting threshold values. The nonlinear optical limiting threshold values of complexes 2, 3 and 4 showed improvement in the solid state (thin films), with complex 4 giving the best value at 0.033 J cm−2. , Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.05.022
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The Photophysical Properties of Multi-Functional Quantum Dots-Magnetic Nanoparticles—Indium Octacarboxyphthalocyanine Nanocomposite
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7248 , http://hdl.handle.net/10962/d1020254
- Description: This work presents the development of a multifunctional hybrid nanoparticle made of L-glutathione capped quantum dots (GSH-CdSe@ZnS), amino functionalized Fe3O4 magnetic nanoparticles and indium octacarboxy phthalocyanine (ClInPc(COOH)8). In this work we investigate the photophysical properties of the individual components and the hybrid nanoparticle, in addition we study the energy transfer (Förster Resonance Energy Transfer (FRET)) in the complex. FRET efficiencies of ~48 % were obtained for energy transfer between the QDs (when alone or linked to MNPs). Both triplet yields and lifetimes of ClInPc(COOH)8 increase in the nanocomposite, with a decrease in fluorescence lifetime. The hybrid nanoparticle showed improved photophysical properties and as a result can be used in photodynamic therapy. , Original publication is available at http://dx.doi.org/10.1007/s10895-014-1497-6
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The use of phthalocyanines in cancer therapy
- Authors: Nyokong, Tebello , Gledhill, Igle
- Language: English
- Type: Article
- Identifier: vital:7323 , http://hdl.handle.net/10962/d1020572
- Description: Phthalocyanines are synthetic analogues of porphyrins employed as photosensitizers in cancer therapy. We present the history of photodynamic therapy and developments in the use of phthalocyanines as photosensitizers. New efforts in the development of more cancer-specific phthalocyanines are presented. The combination of phthalocyanines with nanoparticles for "combination therapy" of cancer is also discussed. The nanoparticles employed are quantum dots, gold, and magnetic nanoparticles. , Original publication is available at http://dx.doi.org/10.10631.4794220
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Tuning the physico-electrochemical properties of novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine complex using phenylamine-functionalised SWCNTs
- Authors: Agboola, Bolade Oyeyinka , Ozoemena, Kenneth I. , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Language: English
- Type: Article
- Identifier: vital:7238 , http://hdl.handle.net/10962/d1019689
- Description: The integration of phenylamine-functionalised SWCNTs (SWCNT-phenylamine) with a novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine (CoOBPPc) complex has been described. The physical and electrochemical properties of the CoOBPPc-SWCNT-phenylamine hybrid were evaluated using spectroscopy (IR and UV–vis), field emission scanning electron microscopy and electrochemistry (cyclic voltammetry and electrochemical impedance spectroscopy). Integration of SWCNT-phenylamine resulted in the physical transformation of the CoOBCPPc from the usually bluish colour of cobalt phthalocyanine complexes to a beautiful bright green colour. In addition, the heterogeneous electron transfer kinetics and electrocatalytic properties of the CoOBCPPc were greatly enhanced following the attachment of the SWCNT-phenylamine. The potential electrocatalytic application of the hybrid was tested using β-nicotinamide adenine dinucleotide (NADH) as a model biological analyte. Interestingly, the onset oxidation potential of this analyte was significantly reduced (300 mV) by this hybrid compared to the bare electrode. , Original publication is available at http://dx.doi.org/doi:10.1016/j.carbon.2009.10.023
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Ultrafast Photodynamics of the Indoline Dye D149 Adsorbed to Porous ZnO in Dye-Sensitized Solar Cells
- Authors: Rohwer, Egmont , Richter, Christoph , Heming, Nadine , Strauch, Kerstin , Litwinski, Christian , Nyokong, Tebello , Schlettwein, Derck , Schwoerer, Heinrich
- Language: English
- Type: Article
- Identifier: vital:7326 , http://hdl.handle.net/10962/d1020576
- 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. , Original publication is available at http://dx.doi.org/10.1002/cphc.201200715
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Unsymmetrically Substituted Nickel Triazatetra-Benzcorrole and Phthalocynanine Complexes: Conjugation to Quantum Dots and Applications as Fluorescent “Turn ON” Sensors
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7311 , http://hdl.handle.net/10962/d1020403
- Description: We report on the design and application of fluorescent nanoprobes based on the covalent linking of L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg2+ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg2+ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg2+ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs. , Original publication is available at http://dx.doi.org/10.1007/s10895-013-1317-4
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