Characterization and application of phthalocyanine-magnetic nanoparticle conjugates anchored to electrospun polyamide nanofibers
- Authors: Ledwaba, Mpho
- Date: 2014
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54610 , vital:26593
- Description: This work presents the syntheses, photophysical and photochemical characterization of zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc, 3) and its gadolinium oxide nanoparticle conjugate (4). By means of spectroscopic and microscopic characterization, the conjugation of the ZnTCPPc to the silica coated gadolinium oxide nanoparticles (Si-Gd2O3 NPs, 2) through an amide bond was confirmed. The thermal stability, morphology, nanoparticle sizes and their conjugates with the Pc were studied using ThermoGravimetric Analysis (TGA), Fourier Transform Infrared spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and powder X-ray diffractometry (XRD). Conjugation of ZnTCPPc to the magnetic nanoparticles, proved to have a negligible effect on the photophysical parameters of the phthalocyanine, where a slight decrease in fluorescence and triplet quantum yields and lifetimes was observed. The singlet oxygen quantum yield, however, increased slightly upon conjugation, suggesting that the overall efficiency of the ZnTCPPc as a photosensitizer had improved. Physical mixing of the ZnTCPPc and the silica-coated gadolinium nanoparticles also showed an improvement in the singlet oxygen quantum yield and triplet lifetime, also showing an enhanced efficiency for the photosensitizer and therefore photocatalysis. ZnTCPPc (3) alone and the Pc-gadolinium oxide nanoparticle conjugate (4) were therefore electrospun into nanofibers to create a solid support. The fibers were characterized and their diameter sizes and composition was studied confirming the incorporation of the phthalocyanine and gadolinium oxide nanoparticle. Increased singlet oxygen generation resulted in increased Photodegradation of the environmental pollutant Orange G and the fibers were found to be more efficient as photocatalysts compared to the photosensitizer in solution. The nanomaterial may therefore be applied to the photodegradation of Orange G.
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- Date Issued: 2014
Fabrication, characterization and application of phthalocyanine-magnetite hybrid nanofibers
- Authors: Modisha, Phillimon Mokanne
- Date: 2014
- Subjects: Nanofibers , Nanoparticles , Magnetite
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4500 , http://hdl.handle.net/10962/d1013223
- Description: Magnetic nanoparticles comprising magnetite (Fe3O4) were functionalized with 3-aminopropyl-triethoxysilane forming amino functionalized magnetite nanoparticles (AMNPs). The amino group allows for conjugation with zinc octacarboxyphthalocyanine (ZnOCPc) or zinc tetracarboxyphthalocyanine (ZnTCPc) via the carboxyl group to form an amide bond. A reduced aggregation of ZnTCPc is observed after conjugation with AMNPs. The thermal stability, conjugation, morphology and the sizes of the nanoparticles and their conjugates were confirmed using thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and Powder X-ray diffractometry (PXRD), respectively. The covalent linkage of AMNPs to ZnOCPc or ZnTCPc resulted in improvement in the photophysical behavior of the phthalocyanines. Improvement in the triplet quantum yield (ΦT), singlet oxygen quantum yield (ΦΔ), triplet lifetime (τT) and singlet oxygen lifetime (τΔ) of the ZnOCPc or ZnTCPc were observed, hence improving the photosensitizers efficiency. The conjugates comprising of zinc octacarboxyphthalocyanine (ZnOCPc) and AMNPs were electrospun into fibers using polyamide-6 (PA-6). This was used for the photodegradation of Orange-G and compared with ZnOCPc-AMNPs in suspension. For ZnOCPc-AMNPs in suspension, it is noteworthy that the catalyst can be easily recovered using an external magnetic field. The singlet oxygen generation increases as we increase the fiber diameter by increasing the ZnOCPc concentration. The singlet oxygen quantum yield is higher for PA-6/ZnOCPc-AMNPs nanofibers when compared to PA-6/ZnOCPc. The rate of degradation of Orange-G increased with an increase in the singlet oxygen quantum yield. Moreover, the kinetic analysis showed that the photodecomposition of Orange-G is a first-order reaction according to the Langmuir-Hinshelwood model.
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- Date Issued: 2014
Synthesis and characterization of NaYGdF4 upconversion nanoparticles and an investigation of their effects on the spectroscopic properties of two phthalocyanine dyes
- Authors: Taylor, Jessica Mary
- Date: 2014
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54621 , vital:26594
- Description: Sphere and star shaped NaYGdF4:Yb/Er(Tm) upconversion nanoparticles were successfully synthesized utilizing a methanol assisted thermal decomposition approach and their chemical, spectroscopic and fluorescence properties were fully characterized. In addition, their influence on the spectroscopic and fluorescence properties of two phthalocyanines (Pcs) (unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) and aluminium octacarboxy phthalocyanine (Cl)AlOCPc) was investigated. Upconversion nanoparticles were found to produce characteristic upconversion fluorescence emissions in the blue, green, red and NIR regions and were also shown to possess paramagnetic properties. Simple mixing with an H2Pc in toluene was found to exert no change on the spectroscopic or fluorescence properties of the Pc while covalent conjugation to a (Cl)AlOCPc resulted in a large Q band blue shift accompanied by a decrease in fluorescence lifetimes in DMSO. The red light excitation mediated singlet oxygen generation of the H2Pc mixed with upconversion nanoparticles was investigated and singlet oxygen fluorescence lifetimes were found to decrease in the presence of the nanoparticles. Upconversion mediated singlet oxygen generation, by way of resonance energy transfer to the Pc, was also attempted using 972 nm excitation; however, no singlet oxygen was detected utilizing singlet oxygen NIR emission detection. Pending further work using alternative singlet oxygen detection methods, this suggests that while upconversion nanoparticles possess excellent fluorescent imaging capabilities, they are relatively inefficient in inducing singlet oxygen production simply when mixed with phthalocyanines. Despite this, by combining phthalocyanines and upconversion nanoparticles, we present a system capable of: multimodal imaging, using both upconversion and phthalocyanines emissions, singlet oxygen generation, via direct excitation of the phthalocyanine with red laser light, and, possibly, magnetic resonance imaging, as a result of doping the upconversion nanoparticles with Gd3+ ions.
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- Date Issued: 2014