Fluorescence behavior and singlet oxygen generating abilities of aluminum phthalocyanine in the presence of anisotropic gold nanoparticles
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7258 , http://hdl.handle.net/10962/d1020267
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs. , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2014.09.005
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A comparative photophysicochemical study of phthalocyanines encapsulated in core–shell silica nanoparticles
- 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.
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- Date Issued: 2015
Photophysical and nonlinear optical studies of tetraakynyl zincphthalocyanine and its “clicked” analogue
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7251 , http://hdl.handle.net/10962/d1020259
- Description: We report here for the first time on the photophysical and nonlinear optical behavior of tetra-substituted alkynyl zinc phthalocyanine and its “clicked” analogue (4 and 5). The compounds exhibited high triplet quantum yields in dimethylsulphoxide (DMSO). Nonlinear optical (NLO) properties were also evaluated for the two compounds at 532 nm and 10 ns in DMSO. We observed two-photon absorption (2PA) and strong reverse saturable absorption (RSA) as the dominant mechanisms at nanosecond laser excitation. The presence of electron acceptor groups fused with triazole linkers in the peripheral positions of 4 provide excellent coexistent features, such as enhanced triplet quantum yields and lifetimes compared to 5. Large third-order susceptibility (2.09 × 10−11 and 3.53 × 10−9 esu) and hyperpolarizability (1.09 × 10−30 and 9.13 × 10−29 esu) were estimated for complexs 4 and 5, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.01.048
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Synthesis and Photophysical Investigation of Tetraazaporphyrin Substituted with Aggregation‐Induced Emission (AIE) Active Moieties
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
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- Date Issued: 2015
Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7245 , http://hdl.handle.net/10962/d1020250
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 μA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 μA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 μM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine. , Original publication is available at http://dx.doi.org/10.1016/j.jcis.2014.10.056
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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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Enhanced triplet state yields in aqueous media of asymmetric zinc phthalocyanines when conjugated to silver nanoflowers
- Authors: D'Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmus, Mahmut , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189099 , vital:44816 , xlink:href="https://doi.org/10.1016/j.poly.2015.08.017"
- Description: Novel low symmetry water-soluble zinc phthalocyanines (ZnPcs, complexes 1 and 2) were synthesized and then mixed with silver nanoflowers. Photophysical and photochemical studies were performed in order to determine the efficiency of complexes 1 and 2 as photosensitizers when alone and when combined with the silver nanoflowers. The Pcs show low fluorescence quantum yields and excellent triplet quantum yields of 0.78 (for 1) and 0.66 (for 2) in aqueous media. The triplet quantum yield values increased to 0.80 and 0.89, respectively, in the presence of silver nanoflowers. Long triplet lifetimes ranging from 180 to 200 μs in DMSO were obtained for complexes 1, 2 and their conjugates with silver nanoflowers.
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- Date Issued: 2015
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Language: English
- Type: Article
- Identifier: vital:7292 , http://hdl.handle.net/10962/d1020355
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety. , Original publication is available at http://dx.doi.org/10.1142/S1088424615500492
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Iodine-Doped Cobalt Phthalocyanine Supported on Multiwalled Carbon Nanotubes for Electrocatalysis of Oxygen Reduction Reaction
- Authors: Nyoni, Stephen , Mashazi, Philani N , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7242 , http://hdl.handle.net/10962/d1020246
- Description: 4-(4,6-Diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) was iodine doped, and its electrocatalytic properties explored. Physical characterization techniques such as UV-vis, X-ray photoelectron, electron paramagnetic resonance and infra-red spectroscopy were used. Cyclic voltammetry, electrochemical impedance spectroscopy and rotating disk electrode were used for electrochemical characterization of electrodes modified with the prepared phthalocyanine and its nanocomposites. The electrocatalytic effect of a new iodine-doped cobalt phthalocyanine derivative supported on multiwalled carbon nanotubes was then investigated towards oxygen reduction reaction. The electrocatalytic activity of the iodine-doped cobalt phthalocyanine was found to be superior in terms of current over the undoped phthalocyanine nanocomposite. , Original publication is available at http://dx.doi.org/10.1002/elan.201400499
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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
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189763 , vital:44929 , xlink:href="https://doi.org/10.1039/C5RA14916A"
- 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.
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- Date Issued: 2015
The development of Palladium(II)-specific amine-functionalized silica-based microparticles : adsorption and column separation studies
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7270 , http://hdl.handle.net/10962/d1020285
- 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. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
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- Date Issued: 2015
Enhanced triplet state parameters for zinc carboxy phenoxy phthalocyanine following conjugation to ascorbic acid: effects of adsorption on single walled carbon nanotubes
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7265 , http://hdl.handle.net/10962/d1020274
- Description: Zinc phthalocyanine bearing four ascorbic acid units (formed via ester bond between zinc carboxy phenoxy phthalocyanines and ascorbic acid) was synthesized and characterized using different spectroscopic methods. The complex (with or without ascorbic acid) was further adsorbed onto single walled carbon nanotubes (SWCNTs) and further characterized using Raman spectroscopy, X-ray diffractometry, transmission electron microscopy and thermogravimetric analysis. The photophysical properties of the complexes were studied. The synthesized complex showed better photophysical properties when compared to the carboxy phenoxy phthalocyanines alone, this is evident in the increase of the triplet quantum yields (ΦT), triplet life-times (τT) and singlet oxygen quantum yields (ΦΔ). The zinc phthalocyanines bearing ascorbic acid showed improved triplet life-times even in the presence of SWCNTs. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.01.032
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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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Photophysical Properties of Zinc Tetracarboxy Phthalocyanines Conjugated to Magnetic Nanoparticles
- Authors: Modisha, Phillimon , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7254 , http://hdl.handle.net/10962/d1020263
- Description: Magnetite nanoparticles (MNPs) were synthesised by the co-precipitation method and coated with amino functional groups which allowed for amide bond formation with the carboxylic acid groups on zinc tetra- or octa-carboxyphthalocyanine (ZnTCPc or ZnOCPc respectively). The absorption spectra of ZnTCPc linked to MNPs showed a reduction in aggregation, while the photophysical parameters (Φ T , τ T and ΦΔ) of ZnTCPc or ZnOCPc increased upon linking with the MNPs. , Original publication is available at http://dx.doi.org/10.1166/jnn.2015.9247
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Photophysical studies of newly derivatized mono substituted phthalocyanines grafted onto silica nanoparticles via click chemistry
- 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.
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- Date Issued: 2015
Photophysical properties of a new water soluble tetra thiamine substituted zinc phthalocyanine conjugated to gold nanorods of different aspect ratios
- Authors: Mthethwa, Thandekile , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7302 , http://hdl.handle.net/10962/d1020379
- Description: A water soluble zinc phthalocyanine substituted with thiamine is reported in this work. The aggregation of this compound in aqueous solutions causes quenching of the fluorescence quantum yields. Gold nanospheres and nanorods were linked to the phthalocyanine. X-ray photoelectron spectroscopy showed that both the amine and the sulphur groups on the thiamine substituent of the zinc phthalocyanine were involved in the linking to gold nanoparticles. The Pc showed an increase in the fluorescence quantum yields in the presence of the nanoparticles. The singlet oxygen quantum yield increased when the Pc was conjugated to the nanoparticles and even higher for larger aspect ratio gold nanorods. , Original publication is available at http://dx.doi.org/10.1039/C4DT00197D , Arbortext Advanced Print Publisher 9.1.520/W Unicode , Acrobat Distiller 10.0.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
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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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Fluorescence Behaviour and Singlet Oxygen Production of Aluminium Phthalocyanine in the Presence of Upconversion Nanoparticles
- Authors: Watkins, Zane , Taylor, Jessica , D’Souza, Sarah , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7288 , http://hdl.handle.net/10962/d1020337
- Description: NaYF4:Yb/Er/Gd upconversion nanoparticles (UCNP) were synthesised and the photoemission stabilised by embedding them in electrospun fibers. The photophysical behaviour of chloro aluminium tetrasulfo phthalocyanine (ClAlTSPc) was studied in the presence of UCNPs when the two are mixed in solution. The fluorescence quantum yield value of ClAlTSPc decreased in the presence of UCNPs due to the heavy atom effect of UCNPs. This effect also resulted in increase in triplet quantum yields for ClAlTSPc in the presence of UCNPs. The fluorescence lifetimes for UCNPs were shortened at 658 nm in the presence of ClAlTSPc when the former was embedded in fiber and suspended in a dimethyl sulfoxide solution of the latter. A clear singlet oxygen generation by ClAlTSPc though Förster resonance energy transfer was demonstrated using a singlet oxygen quencher, 1,3-diphenylisobenzofuran. , Original publication is available at http://dx.doi.org/10.1007/s10895-015-1632-z
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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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Physicochemical and photodynamic antimicrobial chemotherapy studies of mono- and tetra-pyridyloxy substituted indium(III) phthalocyanines
- Authors: Osifeko, Olawale L , Durmuş, Mahmut , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7255 , http://hdl.handle.net/10962/d1020264 , http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Description: The synthesis and photophysicochemical properties of mono- and tetra-pyridyloxy substituted indium(III) phthalocyanines (InPcs) are presented in this study. General trends are described for quantum yields of fluorescence, triplet, singlet oxygen and photodegradation as well as lifetimes of fluorescence and triplet state of these compounds. The complexes exhibited high singlet oxygen quantum yields (ФΔ) ranging from 0.44 to 0.66 in DMF, and from 0.44 to 0.69 in DMSO and ФΔ = 0.31 for the quartenized tetra substituted InPc which is soluble in water. The triplet quantum yields (ФT) ranged from 0.77 to 0.95 in DMF and from 0.77 to 0.94) in DMSO. The tetra substituted photosensitizers do not differ in their inactivation of bacteria with over 8 log reduction of viable bacteria when compared with the mono substituted photosensitizer which could only manage a 1 log reduction. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
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- Date Issued: 2015