Nonlinear optical responses of phthalocyanines in the presence of nanomaterials or when embedded in polymeric materials
- Authors: Bankole, Owolabi Mutolib
- Date: 2017
- Subjects: Phthalocyanines , Phthalocyanines -- Optical properties , Alkynes , Triazoles , Nonlinear optics , Photochemistry , Complex compounds , Amines , Mercaptopyridine
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/45794 , vital:25548
- Description: This work describes the synthesis, photophysical and nonlinear optical characterizations of alkynyl Pcs (1, 2, 3, 8 and 9), 1,2,3-triazole ZnPc (4), mercaptopyridine Pcs (5, 6 and 7) and amino Pcs (10 and 11). Complexes 1, 2, 4, 7, 8, 9 and 11 were newly synthesized and characterized using techniques including 1H-NMR, MALDI-TOF, UV-visible spectrophotometry, FTIR and elemental analysis. The results of the characterizations were in good agreement with their molecular structures, and confirmed the purity of the new molecules. Complex 10 was covalently linked to pristine graphene (GQDs), nitrogen- doped (NGQDs), and sulfur-nitrogen co-doped (SNGQDs) graphene quantum dots; gold nanoparticles (AuNPs); poly(acrylic acid) (PAA); Fe3O4@Ag core-shell and Fe3O4- Ag hybrid nanoparticles via covalent bonding. Complex 11 was linked to Agx Auy alloy nanoparticles via NH2-Au and/or Au-S bonding, 2 and 3 were linked to gold nanoparticles (AuNPs) via clicked reactions. Evidence of successful conjugation of 2, 3, 10 and 11 to nanomaterials was revealed within the UV-vis, EDS, TEM, XRD and XPS spectra. Optical limiting (OL) responses of the samples were evaluated using open aperture Z-scan technique at 532 nm and 10 ns radiation in solution or when embedded in polymer mixtures. The analyses of the Z-scan data for the studied samples did fit to a two-photon absorption mechanism (2PA), but the Pcs and Pc-nanomaterial or polymer composites also possess the multi-photon absorption mechanisms aided by the triplet-triplet population to have reverse saturable absorption (RSA) occur. Phthalocyanines doped in polymer matrices showed larger nonlinear absorption coefficients (ßeff), third-order susceptibility (Im [x(3)]) and second-order hyperpolarizability (y), with an accompanying low intensity threshold (Ium) than in solution. Aggregation in DMSO negatively affected NLO behaviour of Pcs (8 as a case study) at low laser power, and improved at relatively higher laser power. Heavy atom-substituted Pcs (6) enhanced NLO and OL properties than lighter atoms such as 5 and 7. Direct relationship between enhanced photophysical properties and nonlinear effects favoured by excited triplet absorption of the 2, 3, 10 and 11 in presence of nanomaterials was established. Major factor responsible for the enhanced nonlinearities of 10 in the presence of NGQDs and SNGQDs were fully described and attributed to the surface defects caused by the presence of heteroatoms such as nitrogen and sulfur. The studies showed that phthalocyanines-nanomaterial composites were useful in applications such as optical switching, pulse compressor and laser pulse narrowing.
- Full Text:
- Authors: Bankole, Owolabi Mutolib
- Date: 2017
- Subjects: Phthalocyanines , Phthalocyanines -- Optical properties , Alkynes , Triazoles , Nonlinear optics , Photochemistry , Complex compounds , Amines , Mercaptopyridine
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/45794 , vital:25548
- Description: This work describes the synthesis, photophysical and nonlinear optical characterizations of alkynyl Pcs (1, 2, 3, 8 and 9), 1,2,3-triazole ZnPc (4), mercaptopyridine Pcs (5, 6 and 7) and amino Pcs (10 and 11). Complexes 1, 2, 4, 7, 8, 9 and 11 were newly synthesized and characterized using techniques including 1H-NMR, MALDI-TOF, UV-visible spectrophotometry, FTIR and elemental analysis. The results of the characterizations were in good agreement with their molecular structures, and confirmed the purity of the new molecules. Complex 10 was covalently linked to pristine graphene (GQDs), nitrogen- doped (NGQDs), and sulfur-nitrogen co-doped (SNGQDs) graphene quantum dots; gold nanoparticles (AuNPs); poly(acrylic acid) (PAA); Fe3O4@Ag core-shell and Fe3O4- Ag hybrid nanoparticles via covalent bonding. Complex 11 was linked to Agx Auy alloy nanoparticles via NH2-Au and/or Au-S bonding, 2 and 3 were linked to gold nanoparticles (AuNPs) via clicked reactions. Evidence of successful conjugation of 2, 3, 10 and 11 to nanomaterials was revealed within the UV-vis, EDS, TEM, XRD and XPS spectra. Optical limiting (OL) responses of the samples were evaluated using open aperture Z-scan technique at 532 nm and 10 ns radiation in solution or when embedded in polymer mixtures. The analyses of the Z-scan data for the studied samples did fit to a two-photon absorption mechanism (2PA), but the Pcs and Pc-nanomaterial or polymer composites also possess the multi-photon absorption mechanisms aided by the triplet-triplet population to have reverse saturable absorption (RSA) occur. Phthalocyanines doped in polymer matrices showed larger nonlinear absorption coefficients (ßeff), third-order susceptibility (Im [x(3)]) and second-order hyperpolarizability (y), with an accompanying low intensity threshold (Ium) than in solution. Aggregation in DMSO negatively affected NLO behaviour of Pcs (8 as a case study) at low laser power, and improved at relatively higher laser power. Heavy atom-substituted Pcs (6) enhanced NLO and OL properties than lighter atoms such as 5 and 7. Direct relationship between enhanced photophysical properties and nonlinear effects favoured by excited triplet absorption of the 2, 3, 10 and 11 in presence of nanomaterials was established. Major factor responsible for the enhanced nonlinearities of 10 in the presence of NGQDs and SNGQDs were fully described and attributed to the surface defects caused by the presence of heteroatoms such as nitrogen and sulfur. The studies showed that phthalocyanines-nanomaterial composites were useful in applications such as optical switching, pulse compressor and laser pulse narrowing.
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A study of electrospun nanofibers and diatomaceous earth materials for the extraction of alkaloids, flavonoids and aromatic amines in various matrices
- Mothibedi, Kediemetse (Kedimetse)
- Authors: Mothibedi, Kediemetse (Kedimetse)
- Date: 2013 , 2013-04-07
- Subjects: Nanofibers , Electrospinning , Sorbents , Extraction (Chemistry) , Alkaloids , Flavonoids , Amines , Matrices , Goldenseal , Ginkgo , Dyes and dyeing -- Chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4288 , http://hdl.handle.net/10962/d1003052 , Nanofibers , Electrospinning , Sorbents , Extraction (Chemistry) , Alkaloids , Flavonoids , Amines , Matrices , Goldenseal , Ginkgo , Dyes and dyeing -- Chemistry
- Description: The thesis explored the use of different sorbent materials in solid phase extraction method development. The methods included the use of the polymeric Agilent Bond Elut Plexa solid phase extraction and electrospun polymer-silica composite sorbents for clean-up and preconcentration. Sample clean-up for alkaloids (hydrastine and berberine) in goldenseal, Hydrastis canadensis and flavonoids (quercetin, kaempferol and isorhamnetin) in Ginkgo biloba was achieved using Bond Elut Plexa SPE sorbent. Clean-up of flavonoids in Ginkgo biloba was also achieved using electrospun polymer-silica composite (polystyrene-silica, polyacrylonitrile-silica and nylon 6-silica) sorbents. All analysis of flavonoids and alkaloids was carried out using an Agilent 1200 Series HPLC coupled with a diode array detector. Good peak separation was achieved in less than 6 min employing an Agilent ZORBAX Eclipse Plus C18 column (4.6 x 75 mm, 3.5 μm) at 35⁰C. The mobile phases employed were 0.1% phosphoric acid/methanol gradient and 0.5% phosphoric acid/methanol (40:60) for alkaloids and flavonoids respectively. The calibration curves exhibited linearity up to 120 μg mL⁻¹ with correlation coefficients of more than 0.9980. The recoveries ranged from 73-109% with relative standard deviation of less than 5% for all analytes. Agilent Chem Elut supported liquid extraction was employed for the development of a sample preparation method for the determination of 24 banned aromatic amines from azo dyes in textile following the EU standard method EN 14362-1:2003 (E) and the Chinese standard method GB/T 17592-2006. The supported liquid extraction was effective in the extraction of the aromatic amines from textile (cotton, wool and polyester/cotton [80%:20%]). Most of the recoveries obtained were conforming to the minimum requirements set in the EN 14362-1:2003 (E) standard method and the relative standard deviations were less than 15%. Good peak separation was obtained within 70 min run time using the Agilent Zorbax SB-Phenyl column (4.6 mm x 250 mm, 5-micron) or the Agilent DB-35 MS (J & W) (30 m x 0.25 mm, 0.25 μm film thickness. It was demonstrated that the polymeric Agilent Bond Elut Plexa, electrospun nanofibers and diatomaceous earth were effective in extraction of alkaloids, flavonoids and aromatic amines in different matrices. The developed methods were simple, rapid and reproducible.
- Full Text:
- Authors: Mothibedi, Kediemetse (Kedimetse)
- Date: 2013 , 2013-04-07
- Subjects: Nanofibers , Electrospinning , Sorbents , Extraction (Chemistry) , Alkaloids , Flavonoids , Amines , Matrices , Goldenseal , Ginkgo , Dyes and dyeing -- Chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4288 , http://hdl.handle.net/10962/d1003052 , Nanofibers , Electrospinning , Sorbents , Extraction (Chemistry) , Alkaloids , Flavonoids , Amines , Matrices , Goldenseal , Ginkgo , Dyes and dyeing -- Chemistry
- Description: The thesis explored the use of different sorbent materials in solid phase extraction method development. The methods included the use of the polymeric Agilent Bond Elut Plexa solid phase extraction and electrospun polymer-silica composite sorbents for clean-up and preconcentration. Sample clean-up for alkaloids (hydrastine and berberine) in goldenseal, Hydrastis canadensis and flavonoids (quercetin, kaempferol and isorhamnetin) in Ginkgo biloba was achieved using Bond Elut Plexa SPE sorbent. Clean-up of flavonoids in Ginkgo biloba was also achieved using electrospun polymer-silica composite (polystyrene-silica, polyacrylonitrile-silica and nylon 6-silica) sorbents. All analysis of flavonoids and alkaloids was carried out using an Agilent 1200 Series HPLC coupled with a diode array detector. Good peak separation was achieved in less than 6 min employing an Agilent ZORBAX Eclipse Plus C18 column (4.6 x 75 mm, 3.5 μm) at 35⁰C. The mobile phases employed were 0.1% phosphoric acid/methanol gradient and 0.5% phosphoric acid/methanol (40:60) for alkaloids and flavonoids respectively. The calibration curves exhibited linearity up to 120 μg mL⁻¹ with correlation coefficients of more than 0.9980. The recoveries ranged from 73-109% with relative standard deviation of less than 5% for all analytes. Agilent Chem Elut supported liquid extraction was employed for the development of a sample preparation method for the determination of 24 banned aromatic amines from azo dyes in textile following the EU standard method EN 14362-1:2003 (E) and the Chinese standard method GB/T 17592-2006. The supported liquid extraction was effective in the extraction of the aromatic amines from textile (cotton, wool and polyester/cotton [80%:20%]). Most of the recoveries obtained were conforming to the minimum requirements set in the EN 14362-1:2003 (E) standard method and the relative standard deviations were less than 15%. Good peak separation was obtained within 70 min run time using the Agilent Zorbax SB-Phenyl column (4.6 mm x 250 mm, 5-micron) or the Agilent DB-35 MS (J & W) (30 m x 0.25 mm, 0.25 μm film thickness. It was demonstrated that the polymeric Agilent Bond Elut Plexa, electrospun nanofibers and diatomaceous earth were effective in extraction of alkaloids, flavonoids and aromatic amines in different matrices. The developed methods were simple, rapid and reproducible.
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The development of platinum and palladium-selective polymeric materials
- Authors: Fayemi, Omolola Esther
- Date: 2013 , 2013-05-03
- Subjects: Polymers , Platinum , Palladium , Adsorption , Sorbents , Nanofibers , Amines , Nanoparticles
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4287 , http://hdl.handle.net/10962/d1002964 , Polymers , Platinum , Palladium , Adsorption , Sorbents , Nanofibers , Amines , Nanoparticles
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species (PtCl₆²⁻ and PdCl₄²⁻) on polystyrene-based beads and nanofibers as well as silica microparticles functionalized with polyamine centres derived from ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) is described. The functionalized sorbent materials were characterized by using microanalysis, SEM, XPS, BET and FTIR. The nanofiber sorbent material functionalized with ethylenediamine (F-EDA) had the highest loading capacity which was attributed to its high nitrogen content (10.83%) and larger surface area (241.3m²/g). The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies in 1 M HCI. The adsorption studies for both PtCl₆²⁻ and PdCl₄²⁻ on the polystyrene-based sorbent materials fit the Langmuir isotherm while the silica-based sorbents fitted the Freundlich isotherm with R² values > 0.99. In the column experiment the highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively on the nanofiber sorbent material based on ethylenediamine (EDA). The polystyrene and silica-based resins with triethylenetetramine (TETA) functionality (M-TETA and S-TETA) showed selectivity for platinum and palladium, respectively. Metal chlorido complexes loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as teh eluting agent with quantitative desorption efficiency under the selected experimental conditions. The separation of platinum from palladium was partially achieved by selective stripping of PtCl₆²⁻ with 0.5 M of NaClO₄ in 1.0 M HCI with PdCl₄²⁻ was eluted with 0.5 M thiourea in 1.0 M HCI. The selectivity of the M-TETA and S-TETA sorbent materials was proved by column separation of platinum(IV) and palladium(II), respectively, from synthetic solutions containing iridium(IV) and rhodium(III). The loading capacity for platinum on M-TETA was 0.09 mg/g while it was 0.27 mg/g for palladium on S-TETA. , Acrobat PDFMaker 10.1 for Word , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Authors: Fayemi, Omolola Esther
- Date: 2013 , 2013-05-03
- Subjects: Polymers , Platinum , Palladium , Adsorption , Sorbents , Nanofibers , Amines , Nanoparticles
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4287 , http://hdl.handle.net/10962/d1002964 , Polymers , Platinum , Palladium , Adsorption , Sorbents , Nanofibers , Amines , Nanoparticles
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species (PtCl₆²⁻ and PdCl₄²⁻) on polystyrene-based beads and nanofibers as well as silica microparticles functionalized with polyamine centres derived from ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) is described. The functionalized sorbent materials were characterized by using microanalysis, SEM, XPS, BET and FTIR. The nanofiber sorbent material functionalized with ethylenediamine (F-EDA) had the highest loading capacity which was attributed to its high nitrogen content (10.83%) and larger surface area (241.3m²/g). The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies in 1 M HCI. The adsorption studies for both PtCl₆²⁻ and PdCl₄²⁻ on the polystyrene-based sorbent materials fit the Langmuir isotherm while the silica-based sorbents fitted the Freundlich isotherm with R² values > 0.99. In the column experiment the highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively on the nanofiber sorbent material based on ethylenediamine (EDA). The polystyrene and silica-based resins with triethylenetetramine (TETA) functionality (M-TETA and S-TETA) showed selectivity for platinum and palladium, respectively. Metal chlorido complexes loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as teh eluting agent with quantitative desorption efficiency under the selected experimental conditions. The separation of platinum from palladium was partially achieved by selective stripping of PtCl₆²⁻ with 0.5 M of NaClO₄ in 1.0 M HCI with PdCl₄²⁻ was eluted with 0.5 M thiourea in 1.0 M HCI. The selectivity of the M-TETA and S-TETA sorbent materials was proved by column separation of platinum(IV) and palladium(II), respectively, from synthetic solutions containing iridium(IV) and rhodium(III). The loading capacity for platinum on M-TETA was 0.09 mg/g while it was 0.27 mg/g for palladium on S-TETA. , Acrobat PDFMaker 10.1 for Word , Adobe Acrobat 9.54 Paper Capture Plug-in
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