Conjugation of mono-substituted phthalocyanine derivatives to CdSe@ ZnS quantum dots and their applications as fluorescent-based sensors
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189842 , vital:44936 , xlink:href="https://doi.org/10.1016/j.synthmet.2013.11.016"
- Description: Unsymmetrically substituted derivatives of aluminium amino phthalocyanines were synthesized for the first time, fully characterized and conjugated to CdSe@ZnS quantum dots (QDs). The conjugates were employed as fluorescence-based sensors for anion sensing. Among the anions that enhanced the fluorescence of the probe, fluoride ion was chosen as the test ion to test the efficacy of the probe. Förster resonance energy transfer from the QDs to the phthalocyanine was observed as an indication for the fluorescence quenching of the QDs upon binding to the phthalocyanine. The fluorescence of the linked QDs was progressively enhanced, and linearly proportional to increasing concentrations of fluoride ion. The type of substituent attached to the phthalocyanine ring influenced the efficiency of fluorescence enhancement. The proposed nanoprobe has been employed to detect fluoride ion in cell culture medium and tap water.
- Full Text:
- Date Issued: 2014
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
- Full Text: false
Effects of analytes on the fluorescence properties of CdTe@ ZnS quantum dots decorated with cobalt tetraamino-phthalocyanine
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189829 , vital:44935 , xlink:href="https://doi.org/10.1016/j.jlumin.2013.09.079"
- Description: In this work, we have carried out an investigation on the effects of different biologically active analytes on the fluorescence response of glutathione-capped CdTe@ZnS quantum dots (QDs)-colbalt tetraamino-phthalocyanine nanoconjugate system. Firstly, fluorescence quenching occurred. Experimental results showed that some analytes either “turned on”, others further quenched or showed no effect on the fluorescence emission of the nanoprobe.
- Full Text:
- Date Issued: 2014
Unsymmetrically substituted nickel triazatetra-benzcorrole and phthalocynanine complexes
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189818 , vital:44934 , xlink:href="https://doi.org/10.1007/s10895-013-1317-4"
- 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.
- Full Text:
- Date Issued: 2014
Effects of analytes on the fluorescence properties of CdTe@ZnS quantum dots decorated with cobalt tetraamino-phthalocyanine
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7315 , http://hdl.handle.net/10962/d1020541
- Description: In this work, we have carried out an investigation on the effects of different biologically active analytes on the fluorescence response of glutathione-capped CdTe@ZnS quantum dots (QDs)-colbalt tetraamino-phthalocyanine nanoconjugate system. Firstly, fluorescence quenching occurred. Experimental results showed that some analytes either “turned on”, others further quenched or showed no effect on the fluorescence emission of the nanoprobe. , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2013.09.079
- Full Text: false
Effects of differently shaped silver nanoparticles on the photophysics of pyridylsulfanyl-substituted phthalocyanines
- Authors: D’Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7290 , http://hdl.handle.net/10962/d1020353
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.06.038
- Full Text: false
A comparative photophysicochemical study of mono substituted phthalocyanines grafted onto silica nanoparticles
- Authors: Fashina, Adebayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193844 , vital:45399 , xlink:href="https://doi.org/10.1142/S1088424614500138"
- Description: In this study, we report on the covalent linking of carboxylic acid functionalized silica nanoparticles with zinc phthalocyanine mono-substituted non-peripherally and peripherally with either a 4-amino phenoxy (1, peripheral and 2, non-peripheral) or an amino group (3 peripheral). The grafting is achieved via the formation of an amide bond between the carboxylic acid of the silica nanoparticles and the amino group of the phthalocyanine complexes. The hybrid nanoparticles retained the amorphous nature of silica nanoparticles after conjugation. A slight decrease in fluorescence and a general improvement in triplet quantum yields compared to free Pcs were observed. Triplet lifetimes for 2-SiNPs and 3-SiNPs also improved when compared to the free phthalocyanine. The changes in singlet oxygen quantum yields upon conjugation were minimal.
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- Date Issued: 2014
Photophysical behavior of Zn aminophenoxy substituted phthalocyanine conjugates with carboxylic acid-coated silica nanoparticles
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193802 , vital:45397 , xlink:href="https://doi.org/10.1016/j.molstruc.2014.04.034"
- Description: This work reports on the grafting of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally and peripherally with a 4-amino phenoxy group. The phthalocyanine dyes have free amino groups, facilitating covalent attachment of the dyes on the silica surface via amide bond formation. The surface area of the functionalized silica nanoparticles increased on conjugation but the pore volumes were reduced. The phthalocyanine functionalized silica nanoparticles showed lower fluorescence quantum yields as well as shorter triplet lifetimes compared to the free phthalocyanines in dimethyl formamide. For the non-peripherally substituted phthalocyanines increases in triplet yield quantum yields, lifetimes, and singlet oxygen quantum yields were observed.
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- Date Issued: 2014
Polyamide nanofiber membranes functionalized with zinc phthalocyanines
- Authors: Goethals, Annelies , Mugadza, Tawanda , Arslanoglu, Yasin , Zugle, Ruphino , Antunes, Edith M , Van Hulle, Stijn W , Nyokong, Tebello , De Clerck, Karen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241505 , vital:50945 , xlink:href="https://doi.org/10.1002/app.40486"
- Description: Electrospinning is an efficient method for the production of polyamide nanofiber membranes that are suitable for water filtration. Previous studies have shown that nanofiber membranes have high clean water permeability. The pathogen removal efficiency can be improved by functionalization with (organic) biocides. However, these membranes, like other membranes, are vulnerable to fouling which reduces the filtration efficiency. Therefore the present article investigates the potential of zinc phthalocyanines, which can produce singlet oxygen in the presence of visible light, as a functionalizing agent. The polyamide nanofiber membranes were functionalized with phthalocyanines using both a pre-functionalizing and post-functionalizing method. Only the post-functionalization method shows to result in nanofiber membranes capable of producing singlet oxygen. After 30 min 45% of 1,2-diphenylisobenzofuran (DPBF), used as an oxygen quencher, was removed by reaction with singlet oxygen. This resulted in a removal rate of 0.33 mol DBPF mol−1Zn min−1. During short term leaching tests, phthalocyanines could not be detected.
- Full Text:
- Date Issued: 2014
Polyamide nanofiber membranes functionalized with zinc phthalocyanines
- Authors: Goethals, Annelies , Mugadza, Tawanda , Arslanoglu, Yasin , Zugle, Ruphino , Antunes, Edith M , Hulle, Stijn W H Van , Nyokong, Tebello , Clerck, Karen De
- Language: English
- Type: Article
- Identifier: vital:7313 , http://hdl.handle.net/10962/d1020539
- Description: Electrospinning is an efficient method for the production of polyamide nanofiber membranes that are suitable for water filtration. Previous studies have shown that nanofiber membranes have high clean water permeability. The pathogen removal efficiency can be improved by functionalization with (organic) biocides. However, these membranes, like other membranes, are vulnerable to fouling which reduces the filtration efficiency. Therefore the present article investigates the potential of zinc phthalocyanines, which can produce singlet oxygen in the presence of visible light, as a functionalizing agent. The polyamide nanofiber membranes were functionalized with phthalocyanines using both a pre-functionalizing and post-functionalizing method. Only the post-functionalization method shows to result in nanofiber membranes capable of producing singlet oxygen. After 30 min 45% of 1,2-diphenylisobenzofuran (DPBF), used as an oxygen quencher, was removed by reaction with singlet oxygen. This resulted in a removal rate of 0.33 mol DBPF mol−1Zn min−1. During short term leaching tests, phthalocyanines could not be detected. , Original publication is available at http://dx.doi.org/10.1002/app.40486
- Full Text: false
Effects of redox mediators on the catalytic activity of iron porphyrins towards oxygen reduction in acidic media
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated.
- Full Text:
- Date Issued: 2014
Spectral properties and photophysical behaviour of water soluble cationic Mg (II) and Al (III) phthalocyanines
- Authors: Idowu, Mopelola A , Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241549 , vital:50949 , xlink:href="https://doi.org/10.2478/s11532-013-0388-z"
- Description: Peripherally and non-peripherally tetrasubstituted-[(N-methyl-2-pyridylthio)]phthalocyaninato magnesium (II) (5 and 6) and chloro aluminium (III) (7 and 8) tetraiodide have been synthesized and characterized. The photophysical properties of the complexes in dimethyl sulfoxide (DMSO) and aqueous medium in the presence and absence of cremophore EL have been studied. These complexes show high solubility in aqueous medium though they were aggregated. The triplet state quantum yields (FT) and the triplet lifetimes (tT) were found to be higher in DMSO with ΦT ranging from 0.32 to 0.51, while tT ranged from 282 to 622 ms in DMSO, compared to aqueous medium (pH 7.4 buffer) where ΦT ranged from 0.15 to 0.19 and tT from 26 to 35 ms. Addition of cremophore EL in aqueous solution resulted in partial disaggregation and increased photoactivity. The fluorescence lifetimes of the complexes showed strong dependence on their immediate environment. The ionic magnesium(II) and aluminium(III) phthalocyanines strongly bind to bovine serum albumin (BSA).
- Full Text:
- Date Issued: 2014
Spectral properties and photophysical behaviour of water soluble cationic Mg(II) and Al(III) phthalocyanines
- Authors: Idowu, Mopelola A , Arslanoglu, Yasin , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7277 , http://hdl.handle.net/10962/d1020292
- Description: Peripherally and non-peripherally tetrasubstituted-[(N-methyl-2-pyridylthio)]phthalocyaninato magnesium (II) (5 and 6) and chloro aluminium (III) (7 and 8) tetraiodide have been synthesized and characterized. The photophysical properties of the complexes in dimethyl sulfoxide (DMSO) and aqueous medium in the presence and absence of cremophore EL have been studied. These complexes show high solubility in aqueous medium though they were aggregated. The triplet state quantum yields (FT) and the triplet lifetimes (tT) were found to be higher in DMSO with ΦT ranging from 0.32 to 0.51, while tT ranged from 282 to 622 ms in DMSO, compared to aqueous medium (pH 7.4 buffer) where ΦT ranged from 0.15 to 0.19 and tT from 26 to 35 ms. Addition of cremophore EL in aqueous solution resulted in partial disaggregation and increased photoactivity. The fluorescence lifetimes of the complexes showed strong dependence on their immediate environment. The ionic magnesium(II) and aluminium(III) phthalocyanines strongly bind to bovine serum albumin (BSA). , Original publication is available at http://dx.doi.org/10.2478/s11532-013-0388-z
- Full Text: false
Photocatalytic behavior of phthalocyanine-silver nanoparticle conjugates supported on polystyrene fibers
- Authors: Khoza, Phindile , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7317 , http://hdl.handle.net/10962/d1020561
- Description: Herein, carbazole derivatized non-peripheral (1,(4)-tetra(carbazol-2-yloxy)phthalocyaninatozinc(II), 3-TCbZnPc) and peripheral (2,(3)-tetra(carbazol-2-yloxy)phthalocyaninato zinc(II), 4-TCbZnPc) are conjugated to silver nanoparticles and their photochemical and photophysical behavior are reported. The presence of silver nanoparticles resulted in reduced fluorescence, and increased triplet and singlet oxygen quantum yields. The conjugates were further electrospun into polystyrene fibers, and employed for the photodegradation of methyl orange. The photodegradation of methyl orange using all functionalized fibers followed first order kinetics, and was faster when the conjugates with silver nanoparticles were used. The non-peripherally substituted 3-TCbZnPc gave better photocatalytic activity compared to its peripherally substituted counterpart (4-TCbZnPc). The hybrid electrospun fibers provide great potential as active photocatalysts for degrading organic pollutants. , Online publication is available at http://dx.doi.org/10.1016/j.molcata.2014.07.031
- Full Text: false
Photophysichochemical behavior of carbazole derivatized zinc phthalocyanine in the presence of ZnO microparticles and when embedded in electrospun fibers
- Authors: Khoza, Phindile , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193860 , vital:45400 , xlink:href="https://doi.org/10.1016/j.dyepig.2013.12.019"
- Description: The synthesis of a zinc phthalocyanine complex tetrasubstituted with carbazole functionality at the peripheral position (complex 4) is reported. The singlet oxygen quantum yield of the complex was found to be 0.83 in dimethylformamide (DMF). The complex was subsequently conjugated to zinc oxide microparticles (ZnOMPs), the conjugation (formation of the amide bond) was confirmed by IR spectroscopy. The presence of ZnOMPs was found to reduce the singlet oxygen produced (ΦΔ = 0.63) in DMF. Polystyrene electrospun fibers of complex 4 alone and its conjugate to ZnOMPs were found to be thermally stable. The singlet oxygen quantum yield of the modified electrospun fibers was determined in aqueous media with ADMA as a singlet oxygen quencher and were 0.25 and 0.20 for complex 4 and 4-ZnOMPs embedded in fibers, respectively.
- Full Text:
- Date Issued: 2014
Photophysichochemical behavior of carbazole derivatized zinc phthalocyanine in the presence of ZnO microparticles and when embedded in electrospun fibers
- Authors: Khoza, Phindile , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7303 , http://hdl.handle.net/10962/d1020380
- Description: The synthesis of a zinc phthalocyanine complex tetrasubstituted with carbazole functionality at the peripheral position (complex 4) is reported. The singlet oxygen quantum yield of the complex was found to be 0.83 in dimethylformamide (DMF). The complex was subsequently conjugated to zinc oxide microparticles (ZnOMPs), the conjugation (formation of the amide bond) was confirmed by IR spectroscopy. The presence of ZnOMPs was found to reduce the singlet oxygen produced (ΦΔ = 0.63) in DMF. Polystyrene electrospun fibers of complex 4 alone and its conjugate to ZnOMPs were found to be thermally stable. The singlet oxygen quantum yield of the modified electrospun fibers was determined in aqueous media with ADMA as a singlet oxygen quencher and were 0.25 and 0.20 for complex 4 and 4-ZnOMPs embedded in fibers, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.dyepig.2013.12.019
- Full Text: false
Photocatalytic behavior of phthalocyanine-silver nanoparticle conjugates supported on polystyrene fibers
- Authors: Khozile, Phindile , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189909 , vital:44946 , xlink:href="https://doi.org/10.1016/j.molcata.2014.07.031"
- Description: Herein, carbazole derivatized non-peripheral (1,(4)-tetra(carbazol-2-yloxy)phthalocyaninatozinc(II), 3-TCbZnPc) and peripheral (2,(3)-tetra(carbazol-2-yloxy)phthalocyaninato zinc(II), 4-TCbZnPc) are conjugated to silver nanoparticles and their photochemical and photophysical behavior are reported. The presence of silver nanoparticles resulted in reduced fluorescence, and increased triplet and singlet oxygen quantum yields. The conjugates were further electrospun into polystyrene fibers, and employed for the photodegradation of methyl orange. The photodegradation of methyl orange using all functionalized fibers followed first order kinetics, and was faster when the conjugates with silver nanoparticles were used. The non-peripherally substituted 3-TCbZnPc gave better photocatalytic activity compared to its peripherally substituted counterpart (4-TCbZnPc). The hybrid electrospun fibers provide great potential as active photocatalysts for degrading organic pollutants.
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- Date Issued: 2014
Synthesis and characterization of quantum dots designed for biomedical use
- Authors: Kuzyniak, Weronika , Adegoke, Oluwasesan , Sekhosana, Kutloana E , D'Souza, Sarah , Tshangana, Sesethu Charmaine , Hoffmann, Björn , Ermilov, Eugeny A , Nyokong, Tebello , Höpfner, Michael
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241516 , vital:50946 , xlink:href="https://doi.org/10.1016/j.ijpharm.2014.03.037"
- 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.
- Full Text:
- Date Issued: 2014
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
- Full Text: false
Trends in the TD-DFT calculations of porphyrin and phthalocyanine analogs
- Authors: Mack, John , Stone, Justin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193882 , vital:45402 , xlink:href="https://doi.org/10.1142/S108842461450045X"
- Description: In 2005, Kobayashi and coworkers reported trends in the TD-DFT spectra of 17 Zn (II) porphyrinoids [J. Am. Chem. Soc. 2005; 127: 17697] that were analyzed using Michl's perimeter model as part of a study of the anomalous magnetic circular dichroism (MCD) spectroscopy of zinc tetraphenyltetraacenaphthoporphyrin. In recent years, it has become increasingly clear that TD-DFT calculations with the commonly used hybrid B3LYP exchange-correlation functional of the Gaussian software package are problematic in the B-band region of porphyrinoid spectra, since the degree of configurational interaction between the B and higher energy ππ* state appears to be significantly overestimated. The CAM-B3LYP functional is now often preferred for analyzing the optical properties of porphyrinoids, since it includes a long-range correction of the exchange potential, which incorporates an increasing fraction of Hartree–Fock (HF) exchange as the interelectronic separation increases, making it better suited for studying compounds where there is significant charge transfer in the electronic excited states. The trends in the TD-DFT calculations are reexamined with a wider range porphyrinoid compounds including several with pyrazino moieties and are found to provide a closer agreement with the experimental in the B-band region for complexes such as zinc tetraphenylporphyrin and phthalocyanine.
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- Date Issued: 2014