Design and fabrication of components of dye sensitised solar cells
- Authors: Msane, Gugu
- Date: 2019
- Subjects: Dye-sensitized solar cells
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/117106 , vital:34478
- Description: In recent decades there has been increasing global concern about the sustainability of our use of fossil fuels, which has led to increased interest in carbon–free sustainable renewable sources such as solar energy. Dye sensitized solar cells (DSSCs) are a cheap and clean technology that harnesses solar energy efficiently and convert it to electrical energy. A DSSC consists of a transparent working electrode coated with a dye-sensitized mesoporous film of nanocrystalline particles of semiconductor e.g. TiO2, an electrolyte containing a suitable redox couple and a platinized counter electrode. All the components of the DSSCs play vital roles in controlling the performance of the cell. The synergy of these components of the cells also needs to be investigated to optimise their interaction and create efficient and stable DSSCs. The information gathered from this investigation can give insight on how to improve the efficiencies of DSSCs. In this research study the semiconductor, transparent conducting layer and sensitizer were designed, optimized one at a time and their effect on the overall efficiency of the DSSCs studied. In this way it was easy to observe the effect of the individual components on the efficiency of the DSSCs. The conventional DSSCs usually use TiO2 as a semiconductor. In this research TiO2 was doped with cerium (Ce) to enhance its optical properties by reducing the band gap. A series of Ce-doped TiO2 with Ce content ranging from 0.1 to 1 mol % were successfully synthesized by an acid catalyzed sol-gel method, and their performance as the photoanodes of dye-sensitized solar cells (DSSCs) was investigated. Ce doping resulted in a red shift in the absorption of the TiO2 indicating narrowing of the band gap. The band gap first narrowed with increase in concentration of dopant up until 0.9 % dopant concentration. After this optimum doping concentration the band gap widened again. DFT calculations showed that Ce doping introduces Ce4f impurity states located just below the conduction band resulting in band gap narrowing. Ce content (0.9%) doped TiO2 photoanodes improved the performance of DSSCs with a conversion efficiency of 2.11% compared to 0,21% for the one with a pure TiO2 under 1 sun, AM1.5. Graphitised/TiO2 nanocomposites were also used a semiconductor to slow down recombination of electrons and holes in the cells. Electrophoretic deposition (EPD) was used to deposit graphitised/TiO2 nanocomposites onto an FTO electrode for application as photoelectrode in dye-sensitized solar cells (DSSCs). An enhanced power conversion efficiency (PCE) of 2.25% was observed for the 0.5 wt% graphene oxide/TiO2 (GO/TiO2) based DSSC which was higher than that of the conversion efficiency of pure TiO2 nanoparticles (i.e. 0.52%). Graphene oxide led to high migration of photoinduced electrons to the conduction band of the collection electrode and inhibition of charge carriers recombination resulting in enhanced photoconversion efficiency. A GO content above 0.5 % resulted in a reduced transparency leading to a decrease in the PCE. 0.5 wt % GO/0.9 Ce–TiO2 Ce based DSSC showed a slightly enhanced efficiency of 2.45%. 0.5 rGO/TiO2 based DSSCs had a high efficiency than 0.5 rGO/TiO2 due to improved conductivity of rGO nanosheets and suppressed recombination of charge carriers. To cut down DSSC production costs a silver wire network transparent conducting polyethylene electrodes was fabricated and used as an indium tin oxide (ITO) alternative substrates in DSSCs. The transmittance of the AgNW network was 82 % which is comparable to ITO substrates. Titanium oxide (TiO2) films on the AgWN/PET substrates were obtained using the electrophoresis method. These substrates were sensitised and used to fabricate a dye sensitised solar cell. From the measured current–voltage or I-V characteristic under AM1.5 illumination of the formed DSSC using AgWN substrates, an open circuit voltage (VOC) of 0.377 V, a short circuit current (ISC) of 0.0067 mA and a fill factor (FF) 25.7 % with an efficiency of 0.00862 % were obtained from a cell of 0.075 cm2 working area. The stability of the cell improved when a room temperature ionic liquid electrolyte was used. Gold nanofiber transparent electrodes were also prepared by the electrospinning techniques and used as an alternative to indium tin oxides substrates. Transparent conducting gold nanofiber (AuNF) transparent conducting electrodes were fabricated by using a low–cost electrospinning process and used as photoelectrodes for DSSCs. TiO2 was deposited on these electrodes by using an electrospray method. DSSC using AuNF as transparent electrodes had a power efficiency of 0.52%, compared to devices made with FTO electrodes (1.48%). DSSCs. Versatile dyes with increased spectral response, stability and suppressed recombination of holes and electrons were synthesised and used as a sensitizers for DSSCs. The boron dipyrrin (BODIPY) chromophore was combined with a carboxy coumarin moiety to create donor–acceptor (dyad) system dyes. Regenerative dyad dyes were formed through covalently linking a porphyrin chromophore to a manganese(II) ion through bridging ligands. These chromophores and also porphyrin and BODIPY dyes were used as sensitisers for DSSCs. The regenerative dye based DSSCs showed a photoconversion efficiency of 4.09% which was higher than the efficiency of the parent porphyrin (2.57%). The enhanced efficiency was attributed to the manganese bypridine cluster in the ZnTPP–Mn bpy supramolecule which acted as an electron donor to the photo-oxidized porphyrin continuously regenerating the porphyrin and preventing its decay.
- Full Text:
Ph-responsive liposomal systems for site-specific pulmonary delivery of anti-tubercular drugs
- Authors: Nkanga, Christian Isalomboto
- Date: 2019
- Subjects: Tuberculosis -- Chemotherapy , Lipsomes , Drug carriers (Pharmacy) , Rifampin , Hydrogen-ion concentration , Hydrogen-ion concentration -- Physiological effect
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/125832 , vital:35822
- Description: Tuberculosis (TB) is an infectious disease that has been reported to be the ninth leading cause of death worldwide, even though mostly considered as a poverty related disease. Despite the existence of potent anti-tubercular drugs (ATBDs), such as rifampicin (RIF) and isoniazid (INH), TB remains the major killer among many microbial diseases over the last five years. Although several factors are to be blamed for this deadly status, the most crucial issues encompass both the self-defensiveness of the causative agent (Mycobacterium tuberculosis), including its intra-macrophage location that compromises ATBDs accessibility, and the widespread/off target distribution of ATBDs. The need for novel drug delivery strategies therefore arises to provide selective distribution of ATBDs at the infected site. Among the drug vehicles explored in this field, liposomes have been reported to be the most suitable drug carriers due to their rapid uptake by alveolar macrophages, where M. tuberculosis often resides. Since liposomes experience media of different pH throughout the cell uptake process (endocytosis/phagocytosis), the use of pH change as a stimulus for controlled release looks promising for enhancing intra-macrophage delivery and minimizing premature ‘off-target’ release of ATBDs. However, the costly status of liposome technology, due to the use of sophisticated procedures and expensive materials (especially for pH-dependent delivery, where special lipids are required), may preclude wider developments of liposomal products, especially for the developing world. This study aimed at investigating liposomal encapsulation of pH-sensitive and fluorescent hydrazone derivatives of INH using crude soybean lecithin, as a cost-effective option for site-specific delivery combined with potential bio-imaging features. Another objective was to explore encapsulation of INH hydrazone derivatives with and without RIF in liposomes using a simple and organic solvent-free preparation method. Initially, INH was coupled with 4-hydroxy-benzaldehyde to yield a conjugate (INH-HB) that was encapsulated in liposomes using film hydration method with acceptable encapsulation efficiency (î), about 89 %. The prepared INH-HB loaded liposomes (IHL) were characterized by means of dynamic light scattering (DLS), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The release of INH from IHL was evaluated over 12 hours in media of different pH using dialysis. As hypothesized, pH dependent release of INH from IHL was observed with 22, 69, 83 and 100 % release obtained in media of pH 7.4, 6.4, 5.4 and 4.4, respectively. From this experimental trial, further development was undertaken by conjugating INH to a hydrophobic fluorescent tag, zinc (II) phthalocyanine (PC), through hydrazone linkages. The obtained conjugate (PC-INH) was loaded into liposomes (PIL) that were characterized using various spectroscopic techniques, including UV-Vis absorption and energy dispersive X-ray spectroscopy, which suggested the presence of PC-INH within the lipid bilayers. The release study performed in different pH media revealed 22, 41, 97 and 100 % of INH, respectively released at pH 7.4, 6.4, 5.4 and 4.4. This confirmed the potential of pH-triggered drug release from liposomes loaded with hydrazone drug derivatives. In addition, successful encapsulation of PC-INH using crude soybean lecithin inspired a new opening towards development of multimodal liposomes that could achieve controlled drug release with added benefits of image-guided biological tracking. However, the hydrophobic nature of PC-INH requires an effective strategy that could improve its solubility and favour extensive development. In this context, the tetra-substituted structure of PC-INH brought up the hypothesis that cyclodextrin (CD) complexation would facilitate PC-INH encapsulation in liposomes using an organic solvent-free method, called here the “heating method” (HM). Inclusion complexes of PC-INH with various CDs were therefore investigated, with gamma-CD complex (CP) giving the best results. These complexes were prepared in both solution and solid-state and further comprehensively characterized using UV-Vis spectroscopy, magnetic circular dichroism, NMR spectroscopy, diffusion ordered spectroscopy, DSC, XRD and Fourier transform infrared spectroscopy. CP-loaded liposomes prepared using HM exhibited greater î than film hydration liposomes, about 70 % versus 56 %, respectively. The HM-liposomal system (CPL) exhibited potentially useful nano particulate characteristics (i.e. mean particle size 240 nm and Zeta potential –57 mV), which remained unchanged over 5 weeks of stability study at 4 °C, and pH-dependent INH release behaviour alike PIL. Furthermore, CP was co-encapsulated with rifampicin (RIF) in liposomes using HM to investigate the possibility for future combination therapy. 1H-NMR spectroscopy, DSC, XRD and photophysical studies were performed for molecular assessment of the cargo in CP-RIF co-loaded liposomes (CPRL). The mean particle size, Zeta potential and î of CPRL were respectively 594 nm, –50 mV, 58 % for CP and 86 % for RIF. CPRL exhibited much higher release rates for both INH and RIF at pH 6.4, compared to those tested at pH 7.4. In addition, there was no cytotoxicity on HeLa cells, but attractive lung fibroblasts and epithelial cells uptake and viability. Hence, CPRL are promising for targeted ATBD delivery to alveolar macrophages following pulmonary administration. Overall, the developed pH-responsive liposomal system holds the promise for new openings towards wider developments of multifunctional liposomes for site-specific controlled pulmonary delivery of antimicrobials drugs.
- Full Text:
Synthesis of pH responsive carriers for pulmonary drug delivery of anti-tuberculosis therapeutics: mesoporous silica nanoparticles and gelatin nanoparticles
- Authors: Ngoepe, Mpho Phehello
- Date: 2019
- Subjects: Drug delivery systems , Pulmonary pharmacology , Nanosilicon , Nanomedicine , Nanoparticles , Mesoporous materials , Silica , Tuberculosis -- Treatment
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76519 , vital:30590
- Description: Pulmonary drug delivery has historically been used as a route for delivery of therapeutics for respiratory disease management. However, while there are many advantages, there are also some serious limitations, arising mostly from the physical aspects of the inhaler devices. This is more profound when the devices are the driving force for controlling particle size generation, which results in non-uniform particles that end up being swallowed/wasted/expelled. One promising solution to overcome this limitation is to pre-formulate nano/microscale particles with a high degree of manufacturing control. Nanomedicine has advanced such that there are already several nanoparticle formulations commercially available. In the case of tuberculosis treatment, there is an opportunity not only to examine the use of nanoparticles for inhalation therapy, but to take advantage of the fact that the physiochemical environment of diseased tissue is significantly different to health lung tissue (lower pH and increased enzyme concentrations). We formulated two series of nanoparticles, whose design included moieties that could respond to pH and enzymes. To address variability, a Box-Behnken statistical approach was followed to construct mesoporous silica nanoparticles. These “hard nanoparticles” can entrap both lipophilic and hydrophilic drugs and were coated with a pH-sensitive hydrazone linker. It was observed that pH, calcination temperature and ratio of water to silica source played the greatest role, not only in controlling the physicochemical properties of the nanoparticles but also the drug release rate. A second series of nanoparticles were synthesized based on gelatin. This was done partly to add support the comparison of hard (inorganic silica) versus soft, organic particles, but also to enable enzymatic degradation and drug release. Again, diseased lung tissue expresses increased concentrations of gelatinase enzymes that could be used to stimulate drug release at the site of the disease. In addition, it was observed that the non-ionic surfactant C12E10 could interact with the protein via hydrophobic interactions thus affecting the gelatin folding. The folding states affected crosslinking with the pH responsive linker, which in turn affected the rate of drug release. To support the synthetic work, we sought to develop a unique 3D lung model directly from MRI data of tuberculosis infected lungs. This would not only permit the evaluation of our nanoparticles but could be used as a proxy for in-vivo studies in future to predict lung deposition in diseased lung. Thus, this study shows that it is possible to synthesize pH and enzyme sensitive nanoparticles for pulmonary drug delivery in the treatment and management of pulmonary tuberculosis. These particles could be loaded with either hydrophobic or hydrophilic drugs and their distribution in the airway modelled using an in-silico 3D model based on real data. Further development and verification of these results should improve treatment for pulmonary diseases and conditions such as tuberculosis. This is especially urgent in the face of multi-drug resistance and poor side effects profiles for current treatment.
- Full Text: