Photophysical properties of a series of alloyed and non-alloyed water-soluble l-cysteine-capped core quantum dots
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188486 , vital:44758 , xlink:href="https://doi.org/10.1016/j.jallcom.2016.10.276"
- Description: Photophysical properties of quantum dots (QDs) such as their photoluminescence (PL) quantum yield (QY), exciton lifetime and PL stability are important parameters used to unravel their chemical and physical characteristics. In this work, we have comparatively investigated the photophysical properties of a series of L-cysteine-capped non-alloyed (CdTe and CdSe) and alloyed (CdZnTe, CdSeS, CdSeTe and CdSeTeS) core QDs. Each of the QDs varied in their size and PL emission wavelength. We observe no physical relationship between the PL QY of the QDs and their PL stability. Based on the PL stability assessment, CdTe QDs with a high PL QY value of 88% exhibited poor PL stability while moderate PL stability was observed for CdZnTe (QY = 78%); CdSe (QY = 3%); and CdSeTe QDs (QY = ∼3%). Alloyed CdSeS (QY = ∼69%) and CdSeTeS (QY = 23%) QDs exhibited good PL stability and can serve as potential fluorophores for a wide range of chemical and biological applications. Generally, it is proposed that the structural nature of the QDs played a significant role in their overall photophysical properties. The information provided in this work will assist in the selection of core QDs suitable for different applications.
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Fluorescence properties of alloyed ZnSeS quantum dots overcoated with ZnTe and ZnTe/ZnS shells
- Authors: Adegoke, Oluwasesan , Mashazi, Philani N , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240754 , vital:50868 , xlink:href="https://doi.org/10.1016/j.optmat.2016.02.024"
- Description: Fluorescent alloyed ternary ZnSeS quantum dots (QDs) have been synthesized via the pyrolysis of organometallic precursors. The effects of passivation of ZnTe and ZnTe/ZnS shells on the optical properties of the ternary alloyed ZnSeS core have been studied. A ligand exchange reaction using L-cysteine as a capping ligand was used to obtain water-soluble nanocrystals. The nanocrystals were each characterized by UV/vis absorption and fluorescence spectroscopy, transmission electron microscopy, X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) quantum yield (QY) of alloyed ZnSeS QDs was 14% and this value increased to 27% when ZnTe was overcoated around the surface but further coating with a ZnS shell decreased the PL QY slightly to 24%. This implies that ZnTe shell suppressed non-radiative recombination exciton states in the alloyed core while further layering with a ZnS shell offered no further improvement in suppressing the defect states. XPS analysis confirmed the presence of the first shell layering but showed a weakened intensity signal of S (2p) and Se (3d) for the ZnSeS/ZnTe/ZnS QDs. Our work demonstrates for the first time that shell passivation of alloyed Zn-based QDs can offer improved optical properties. We hope the optical information presented in this work will be useful in the selection of alloyed Zn-based QDs appropriate for the intended application.
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Optical properties of water-soluble L-cysteine-capped alloyed CdSeS quantum dot passivated with ZnSeTe and ZnSeTe/ZnS shells
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193609 , vital:45352 , xlink:href="https://doi.org/10.1016/j.optmat.2015.05.024"
- Description: Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing L-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed L-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties.
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Structural and optical properties of alloyed quaternary CdSeTeS core and CdSeTeS/ZnS core–shell quantum dots
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193575 , vital:45349 , xlink:href="https://doi.org/10.1016/j.jallcom.2015.05.083"
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface.
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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.
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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.
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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.
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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.
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Fluorescence “switch on” of conjugates of CdTe@ ZnS quantum dots with Al, Ni and Zn tetraamino-phthalocyanines by hydrogen peroxide
- Authors: Adegoke, Oluwasesan , Khene, Samson M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241750 , vital:50966 , xlink:href="https://doi.org/10.1007/s10895-013-1222-x"
- Description: In this study, we have developed a novel nanoprobe for H2O2 based on the conjugation of CdTe@ZnS quantum dots (QDs) to different metal tetraamino-phthalocyanine (MTAPc): (M = (OAc)Al, {OAc = acetate}, Ni and Zn). Chemical coordination of the QDs to the MTAPc resulted in the fluorescence “switch off” of the linked QDs which was associated with Förster resonance energy transfer (FRET). In the presence of varying concentration of H2O2, the fluorescence of the linked QDs was progressively “switched on” and the FRET mechanism between the QDs and the MTAPc was disrupted. The sensitivity/limit of detection of the nanoprobe followed the order: QDs-ZnTAPc (2.2 μM) > QDs-NiTAPc (4.4 μM) > QDs-AlTAPc (9.8 μM) while the selectivity followed the order: QDs-NiTAPc > QDs-AlTAPc > QDs-ZnTAPc. The varying degree of sensitivity/selectivity and mechanism of detection is discussed in detail.
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Fluorescence “turn on” probe for bromide ion using nanoconjugates of glutathione-capped CdTe@ ZnS quantum dots with nickel tetraamino-phthalocyanine
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190479 , vital:44998 , xlink:href="https://doi.org/10.1016/j.jphotochem.2013.05.013"
- Description: In this paper, three differently sized glutathione (GSH)-capped CdTe@ZnS quantum dots (QDs) have been successfully conjugated to nickel tetraamino-phthalocyanine (NiTAPc) to form different QDs-NiTAPc nanocomplexes. Several techniques such as TEM, FT-IR, time-resolved fluorescence measurement and electronic spectroscopy were employed to characterize the nanocomplex. Bromide ion was chosen as a model anion to test the efficacy of the nanoprobe. The fluorescence of the nanoconjugate was “turned off” upon binding but was progressively “turned on” upon interaction with varying concentrations of bromide ion. Experimental results showed that the quantum size effect of nanocrystal QD determined the overall sensitivity and selectivity of the nanoprobe and followed the order QD563-NiTAPc > QD605-NiTAPc > QD621-NiTAPc. The mechanism of reaction is proposed.
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Nanoconjugates of CdTe@ ZnS quantum dots with cobalt tetraamino-phthalocyanine
- Authors: Adegoke, Oluwasesan , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242049 , vital:50996 , xlink:href="https://doi.org/10.1016/j.jphotochem.2013.02.010"
- Description: The covalent linking of thiol-capped CdTe@ZnS QDs with cobalt tetraamino-phthalocyanine (CoTAPc) has been successfully carried out. Several techniques such as time-resolved fluorescence measurements, thermal gravimetric analysis,transmissionelectronmicroscopy andspectrophotometric techniques were employed to characterize the nanoconjugates. Covalent binding of the QDs with CoTAPc resulted in the fluorescence quenching of the former. In the presence of varying concentrations of superoxide anion (O2 •−), the fluorescence of the QDs in the conjugate was gradually enhanced and the detection limits obtained were 2.1 and 2.4 nM for the smaller and larger QDs, respectively. Based on the excellent selectivity displayed by the nanoconjugates towards O2 •− over other biologically active species, a potential nanosensor was developed.
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Probing the sensitive and selective luminescent detection of peroxynitrite using thiol-capped CdTe and CdTe@ ZnS quantum dots
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193757 , vital:45393 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.08.002"
- Description: CdTe and CdTe@ZnS quantum dots (QDs) capped with 3-mercaptopropionic acid (MPA), thioglycolic acid (TGA), or glutathione (GSH) have been employed for the first time as luminescent probes for the sensitive and selective detection of peroxynitrite (ONOO−) in aqueous solution. The sensitivity of the proposed probe followed the order: MPA–TGA–CdTe@ZnS>GSH–TGA–CdTe@ZnS>MPA–CdTe QDs. The varying degree of quenching is elucidated based on the QD–thiolate bond of CdTe@ZnS being more sensitive to oxidation from ONOO− than CdTe. The selectivity of the probe in the presence of co-existing species followed the order: GSH–TGA–CdTe@ZnS>MPA–TGA–CdTe@ZnS>MPA–CdTe QDs. QDs capped with MPA showed less selectivity for ONOO− than GSH. The best limit of detection (LOD) of 12.6 nM was obtained for MPA–TGA–CdTe@ZnS QDs. Time-resolved fluorescence measurements indicated that the interaction between ONOO− and the QDs is static in nature.
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A comparative study on the sensitive detection of hydroxyl radical using thiol-capped CdTe and CdTe/ZnS quantum dots
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242778 , vital:51077 , xlink:href="https://doi.org/10.1007/s10895-012-1089-2"
- Description: Four types of water-soluble luminescent quantum dots (QDs) whose surface was functionlaized with thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), or glutathione (GSH), were investigated for the sensitive and selective detection of hydroxyl radical (●OH) in aqueous media. It was found that the type of capping agent and QD influenced the sensitivity of the probe. The order of sensitivity of the probe was: GSH-CdTe@ZnS > MPA-CdTe@ZnS > TGA-CdTe > MPA-CdTe QDs. Under the optimum conditions, a limit of detection as low as 8.5 × 10-8 M was obtained using GSH-CdTe@ZnS. The effects of foreign reactive oxygen species and the Fenton reactants and products as possible interferences on the proposed probe were negligible for CdTe@ZnS QDs. Besides, experimental results indicated that CdTe@ZnS QDs were more attractive for the selective recognition of ●OH than CdTe QDs. The mechanistic reaction pathway between the QDs and ●OH is proposed.
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CdTe quantum dots functionalized with 4-amino-2, 2, 6, 6-tetramethylpiperidine-N-oxide as luminescent nanoprobe for the sensitive recognition of bromide ion
- Authors: Adegoke, Oluwasesan , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244393 , vital:51253 , xlink:href="https://doi.org/10.1016/j.aca.2012.01.040"
- Description: A novel bromide ion-selective modified nanoprobe sensor based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT)-functionalized CdTe quantum dots (QDs-4AT) has been developed. Fluorescence quenching of the QDs by 4AT was observed. The functionalized QDs-4AT nanoprobe allowed a highly sensitive determination of bromide ion via analyte-induced change in the photoluminescence (fluorescence recovery) of the modified QDs. A detection limit of 0.6 nM of bromide ion was obtained, while the interfering effect of other inorganic cations and anions was investigated to examine the selectivity of the nanoprobe. The linear range was between 0.01 and 0.13 μM. Combined fluorescence lifetime and electron paramagnetic resonance measurements confirmed electron transfer processes between bromide ion and QDs-4AT.
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Interaction of CdTe quantum dots with 2, 2-diphenyl-1-picrylhydrazyl free radical
- Authors: Adegoke, Oluwasesan , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245751 , vital:51402 , xlink:href="https://doi.org/10.1007/s10895-011-1012-2"
- Description: The interaction of 2,2-diphenyl-1-picrylhydrazyl (DPPH●) free radical with thiol-capped CdTe quantum dots (QDs) has been studied by UV–vis spectroscopy, steady state and time resolved fluorescence measurements. Addition of DPPH● radical to CdTe QDs resulted in fluorescence quenching. The interaction occurs through static quenching as this was confirmed by fluorescence lifetime measurements. Time course absorption studies indicates that DPPH● may be reduced by interaction with QDs to the substituted hydrazine form (2,2-diphenyl-1-picrylhydrazine) DPPH-H. The mechanism of fluorescence quenching of CdTe QDs by DPPH● is proposed.
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