In-situ synthesis of gold nanoparticles on graphene quantum dots-phthalocyanine nanoplatforms: First description of the photophysical and surface enhanced Raman scattering behaviour
- Authors: Nwahara, Nnamdi , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187638 , vital:44682 , xlink:href="https://doi.org/10.1016/j.jphotochem.2018.04.011"
- Description: Owing to the need for new low-dimensional molecular assemblies with tailored electronic properties, the current study presents a facile approach for the synthesis and assembly of gold nanoparticles (AuNPs) onto functional graphene quantum dots (GQDs)-phthalocyanines (Pcs) arrays and the investigation of their photophysical and surface enhanced Raman scattering (SERS) properties. The GQDs were functionalized with L-glutathione (GSH) (to form GQDs@GSH) in order to assist coupling to the low symmetry Zn tris–(tert–butyl) mono carboxyphenoxy (propionic acid) phthalocyanine (complex 1) to form 1@GQDs. The affinity of gold (Au) to sulphur (S) was exploited for the assembly of the AuNPs onto 1@GQDs platform to form 1@GQDs-AuNPs. Transmission electron microscopic investigations confirmed the formation of monodispersed, spherical Pc/GQDs@GSH/AuNPs hybrids. The nanocomposite displayed high triplet quantum yields, which translated into high singlet oxygen quantum yield as high as 87%. Furthermore, the formed composites demonstrated strong surface enhanced Raman scattering (SERS) properties with an unprecedented intrinsic maximal enhancement factor of more than 30-fold. These nanostructures also retain more than 90% of their original SERS intensities after a week of storage, displaying superb stability under ambient conditions. These results highlight the remarkable potential of this composite as a unique Raman-based PDT dosimetric agent.
- Full Text:
In-situ synthesis of gold nanoparticles on graphene quantum dots-phthalocyanine nanoplatforms: First description of the photophysical and surface enhanced Raman scattering behaviour
- Authors: Nwahara, Nnamdi , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188183 , vital:44730 , xlink:href="https://doi.org/10.1016/j.jphotochem.2018.04.011"
- Description: Owing to the need for new low-dimensional molecular assemblies with tailored electronic properties, the current study presents a facile approach for the synthesis and assembly of gold nanoparticles (AuNPs) onto functional graphene quantum dots (GQDs)-phthalocyanines (Pcs) arrays and the investigation of their photophysical and surface enhanced Raman scattering (SERS) properties. The GQDs were functionalized with L-glutathione (GSH) (to form GQDs@GSH) in order to assist coupling to the low symmetry Zn tris–(tert–butyl) mono carboxyphenoxy (propionic acid) phthalocyanine (complex 1) to form 1@GQDs. The affinity of gold (Au) to sulphur (S) was exploited for the assembly of the AuNPs onto 1@GQDs platform to form 1@GQDs-AuNPs. Transmission electron microscopic investigations confirmed the formation of monodispersed, spherical Pc/GQDs@GSH/AuNPs hybrids. The nanocomposite displayed high triplet quantum yields, which translated into high singlet oxygen quantum yield as high as 87%. Furthermore, the formed composites demonstrated strong surface enhanced Raman scattering (SERS) properties with an unprecedented intrinsic maximal enhancement factor of more than 30-fold. These nanostructures also retain more than 90% of their original SERS intensities after a week of storage, displaying superb stability under ambient conditions. These results highlight the remarkable potential of this composite as a unique Raman-based PDT dosimetric agent.
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One-pot synthesis of graphene quantum dots–phthalocyanines supramolecular hybrid and the investigation of their photophysical properties
- Authors: Fomo, Gertrude , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188126 , vital:44725 , xlink:href="https://doi.org/10.1007/s10853-017-1539-y"
- Description: The synthesis of graphene quantum dots (GQDs) using organic compounds as carbon sources via bottom-up approaches has been widely developed, whereas their hybrids with other materials have been previously achieved post-synthetically via multi-step procedures. A novel approach for the preparation of supramolecular hybrid conjugates of GQDs and phthalocyanines (Pcs) via an in situ one-step bottom-up route was employed in this study. The as-synthesized GQDs and their Pc conjugates were characterized using different spectroscopic techniques and their photophysicochemical properties evaluated. Notably, the singlet oxygen quantum yields of the Pcs in the presence of GQDs were found to be 0.51 and 0.74 for 1-GQDs and 2-GQDs, respectively, as compared to the Pcs alone (0.18 and 0.70 for complex 1 and 2, respectively). The increase in triplet quantum yield (ΦT) values is complemented by a decrease in fluorescence quantum yield (ΦF). ΦT value of 0.96 obtained for the complex 2 after conjugation with GQDs is better or higher than the value of 0.74 as reported in the literature when complex 2 was conjugated to semiconductor QDs. Hence, this novel approach resulted in the derivation of hybrid materials with potentials for various photophysicochemical applications such as photodynamic therapy and photocatalysis.
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Photo-induced resonance energy transfer and nonlinear optical response in ball-type phthalocyanine conjugated to semiconductor and graphene quantum dots
- Authors: Nwaji, Njemuwa , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187959 , vital:44713 , xlink:href="https://doi.org/10.1039/C7NJ05196D"
- Description: The synthesis of ball-type zinc and gallium phthalocyanines (complexes 2 and 3) and their covalent linkage to glutathione (GSH) and amine functionalized quantum dots QDs) are reported in this work. Furthermore, their photophysical, photo-induced resonance energy transfer and optical limiting responses were investigated. We observed a decrease in the fluorescence quantum yields with a corresponding increase in the triplet quantum yields of the nanoconjugates in comparison to the phthalocyanine complexes alone. The reverse saturable absorption was found to be dependent on the excited state absorption, and the observed limiting threshold ranged from 0.32 to 1.43 J cm−2. Enhanced triplet parameters and nonlinear optical performance were found when the complexes were covalently linked to semiconductor quantum dots compared to carbon based graphene quantum dots.
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Photophysical studies of graphene quantum dots-Pyrene-derivatized porphyrins conjugates when encapsulated within Pluronic F127 micelles
- Authors: Managa, Muthumuni , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187971 , vital:44714 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.09.031"
- Description: Pyrene-derivatized H2, GaCl, and Zn porphyrins were immobilized on graphene quantum dots (GQDs) to form (GQDs-H2TPrP, GQDs-GaClTPrP, and GQDs-ZnTPrP) conjugates through the π-π stacking interaction method followed by encapsulating into Pluronic F127 micelles to form (GQDs-H2TPrP + F127, GQDs-GaClTPrP + F127, and GQDs-ZnTPrP + F127). Spectroscopic evidence shows that the resultant conjugates were stable due to the strong π-π stacking interaction between the GQDs and the porphyrins. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. GQDs-GaClTPrP + F127 showed highest values of the binding constant (Kb). The Stern-Volmer constant (Ksv) for GQDs-ZnTPrP + F127 were the highest compared to other porphyrins derivatives.
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