This dissertation has been focused on the synthesis and characterization of novel functionalized silica mesoporous crystals by using cationic surfactant and co–structure directing agents (CSDA), the central concept of the synthesis method is to build proper organic/inorganic interactions by introducing CSDA into the synthesis system. By using cationic surfactant as template and anionic CSDA, carboxylic group functionalized mesoporous silicas were successfully synthesized. Well ordered 2D p6mm, cubic Fm-3m, mixture of CCP (Fm-3m) and HCP (P63/mmc), and cubic Fd-3m with uniform carboxylic group distribution have been obtained. Besides, we have investigated the Fm-3m/Fd-3m type intergrowth and new type defects observed in the Fd-3m structure using transmission electron microscopy (TEM) and proposed a “polyhedron packing” model. New amphoteric, inorganic amino acid with highly ordered mesopores were synthesized. Uniform distribution of acid and base organic groups on the mesopore surfaces were formed by interactions between the counter charged surfactant head groups and ionic parts of CSDAs. It has been demonstrated that organic (–NH2 and –COOH) pairs incorporated in the mesopore walls behave as natural amino acids, collectively exhibiting an isoelectric point of ~6.0. Moreover, we have demonstrated that the inorganic amino acid is an efficient catalyst for the reaction between aldehydes and carbon nucleophiles.

This work is concerned with the design and synthesis of the cheap, late first row transition metal complexes of Schiff base ligand systems. The prepared complexes readily afford systematic variation in order to probe potency and understand the role of metal, chelating ligands and anionic ligands when carrying out their cytotoxic effect. This study has lead to a better understanding of the action of these classes of complex and will be used to direct the design of new anti-cancer metallopharmaceuticals going forward. This thesis details the synthesis of a library of Schiff base macroacyclic ligands and their novel late first row transition metal complexes with varying anionic counterparts. The creation of a library with several degrees of variability provides a wide array of parameters to afford subtle variation in structure and chemistry e.g. denticity, co-ordination mode, chelate hole size, metal centred redox potentials, hydrolysis rates, co-ordinative saturation, lipophilicity, solubility and more. Complexation of the ligands was carried out by the free ligand and a novel macroacyclic metal template approach using the cheap late first row transition metal salts of Cobalt (II), Nickel (II), Copper (II) and Zinc (II) plus one Ru (III) complex. Structural studies of the 80 generated complexes was carried out by vibrational spectroscopy, elemental analysis, mass spectrometry, magnetic susceptibility and NMR. Single crystal X-ray structures have been determined with 20 reported in this thesis. All ligands act as tridentate ligands in all except one case to form monomeric distorted trigonal-bipyramidal, square-pyramidal or octahedral structures. In the case of zinc nitrate, the ligand L2PhMe acts as a tetradentate ligand to give a distorted octahedral structure. Paramagnetic NMR and solution magnetic susceptibility of paramagnetic complexes was achieved by the Evans NMR method and analysis of the solution NMR showed that L2R and L3R ligands display 2-fold symmetry and are likely either tetradentate in solution or a fast exchange between imine N-donar sites is occurring even down to -65°C. The majority of the resulting complexes of L1R were screened against a panel of three cancer cell lines. Several categories of complex were able to afford structure activity relationships. It was discovered that the ligand is indeed essential for activity of the metal salts against the panel of cell lines and it was largely discovered that the variation in 'tail group' and anionic coordinating ligands played little role in providing a dramatic variation in activity of the metal salt. In general all L1R complexes displayed moderate cytotoxicity showing a trend in activity with respect to the metal in the order RuIII≈CoII>CuII≈ZnII>NiII, over a 6 day exposure to the three cell panel RuIII was shown to be the most potent metal of the L1R series providing IC50 values of 4.6 (0.7) and 7.5 (1.2) μM against the DLD-1 and H460 cell lines respectively, which is Ca. 4.6 and 15 times less potent than cisplatin to the same cell panel respectively. RuIII was also discovered to be the only metal to provide an IC50 value from a 1 hour exposure to the DLD-1 cell panel. The value of 20.4 (3.5) μM is a moderate figure but again Ca. 10 fold less potent than cisplatin for the same test. The L2R and L3R complexes could not be screened by the same comprehension due to their low solubilities. However the lone screen that was possible from the very sparingly soluble complex [CuCl2(L3Bui)] gave the most exciting result and most potent complex of this thesis. After a 6 day exposure, [CuCl2(L3Bui)] gave IC50 values of 4.3 (0.1) and 2.9 (0.1) μM against the DLD-1 and H460 cell lines respectively. These values are merely 4 and 6 fold more than Cisplatin to the same cell lines respectively and demonstrates the potential of this class of complex as cytostatic agents. Further studies utilising a semi-quantitative DNA damaging assay, demonstrated that all first row complexes can damage DNA when in the presence of hydrogen peroxide, with the exception of ZnII complexes. CoII appeared to afford the greatest DNA damage with the most intsense bands for double strand breaks and the CuII complex of the ligand L3Bui also demonstrated a greater DNA damage as opposed to its L1Bui analogue.

This thesis describes the synthesis and investigation of novel anion templated interlocked structures which incorporate the positively charged imidazolium and triazolium binding motifs for applications in anion recognition and sensing. Chapter One introduces the fields of anion supramolecular chemistry and mechanically interlocked structures, focusing on topics of particular relevance to this thesis, including anion recognition, anion sensing and the templated synthesis of interlocked architectures. Chapter Two details the incorporation of the imidazolium motif into the axle components of anion templated rotaxane hosts to achieve selective anion recognition by virtue of their interlocked binding cavities. The effects of exploiting imidazolium motifs with contrasting hydrogen bond donor arrangements and reducing the macrocycle size on the anion recognition properties of such systems were investigated using 1H NMR spectroscopy. Chapter Three reports the work undertaken to utilise fluorescent reporter groups as stoppers in the synthesis of anion sensing rotaxanes. Imidazolium- and triazolium based systems containing either luminescent ruthenium(II) bipyridyl complexes or the organic fluorophore anthracene were prepared and their anion sensing behaviours explored using fluorescence spectroscopy. Synthetic efforts to construct suitable photo-active rotaxanes are detailed. Chapter Four describes investigations of the novel naphthalimide triazolium motif both for use in interlocked molecular motion systems, and for fluorescence sensing applications. The preparation of a naphthalimide triazolium rotaxane, capable of selective, anion-induced, uni-directional shuttling which was investigated extensively using 1H NMR spectroscopy and optically signalled by perturbations in the UV/Vis spectrum, is detailed. Preliminary research studies into the potential to exploit this motif for surface based fluorescence sensing devices are also included. Chapter Five presents research into the utilisation of acyclic receptors displaying considerable binding induced conformational changes for fluorescence anion sensing. The recognition properties of a series of imidazolium-based receptors were studied, whilst the ability of a pyrene appended analogue to signal anion complexation via changes in excimer emission is reported. The control of interpenetrated assembly formation using anion-induced conformational changes within the threading component of a pseudorotaxane is also discussed. Chapter Six provides the experimental procedures and characterisation details for the compounds synthesised in this thesis. Chapter Seven is a summary of conclusions from Chapters Two, Three, Four and Five. Supplementary information relating to titration protocols, crystallographic data and surface studies is provided in the Appendices.

A highly self-ordered hexagonal array of cylindrical pores has been fabricated by anodizing a thin film of Al on substrate and subsequent growth of GaN and InGaN in these nanoholes has been performed. This AAO template-based synthesis method provides a low cost process to fabricate GaN-based nanomaterials fabrication. / Singapore-MIT Alliance (SMA)

Agarose gel was used as a template to prepare zirconium titanium mixed oxide pellets with bimodal porosity. The materials were fully characterized to assess the effect ofZr:Ti ratio on the physical properties. It was found that the metal oxide ratio had an impact on surface acidity, the number of surface hydroxyl groups, the surface area the crystallinity and the mesopore diameter. The oxides were tested for the adsorption of vanadium ions to determine which Zr mole fraction exhibited the highest loading capacity and the fastest kinetics. A comparative study demonstrated that a hierarchical pore structure had enhanced mass transport properties over a monomodal pore structure of similar Zr:Ti composition. / Three porous zirconium titanium oxides (25 mol% Zr) were synthesized using sol-gel chemistry. One of the materials was templated from agarose gel, the second was produced without the use of a template and the third was templated from stearic acid. All three materials varied in pore architecture. Surface modification was performed post-synthetically using propionic acid (a monomer), glutaric acid (a dimer) and three molecular weights of poly(acrylic acid). Higher loading within the inorganic support was obtained for the polymers than for the smaller molecules. It was found that the pore architecture had a strong bearing on the quantity of polymer incorporated into the metal oxide framework and some effect on the rate of polymer adsorption. Thus there is great value in using templates to control pore structure. The materials were subjected to irradiation with 60Co γ-rays to determine the stability of the inorganic support and the organic functionality. / Hybrid materials were prepared by coating five distinct macroporous commercial membranes with zirconium titanium oxide using sol-gel chemistry. Calcination of these templated materials produced oxide membranes which had a suite of macropore and mesopore architectures, pore volumes and surface areas. These differences in physical properties were used to conduct a fundamental study on the relationship between the mesopore size and volume and the capacity for polymer incorporation. It was found that the polymer loading capacity was highly dependent on the pore size and pore volume. As surface area increased, loading capacity decreased, indicating that much of the increased internal surface was inaccessible to the macromolecules. Thus, mesopore diameter and pore volume must be considered when designing a mesoporous solid support. / Hierarchically porous zirconium titanium oxide and carbon zirconium titanium oxide beads with adjustable meso- and macroporosity were prepared in a one-pot, engineering-friendly process. Poly(acrylonitrile) and block copolymer Pluronic F127 were used as structure directing agents. These millimeter sized spheres were fabricated through drop-wise addition of the template-metal alkoxide solution into either water or liquid nitrogen. Carbon zirconium titanium oxide beads were produced by carbonizing the beads at 550 °C in an inert atmosphere. The (carbon) zirconium titanium oxide beads were assessed for surface accessibility and adsorption rate by monitoring the adsorption of uranyl from solution. / Porous metal oxide monoliths, specifically silica, titania, zirconia and mixed oxides containing aluminum and yttrium, were prepared in a one-pot synthesis. Macroporosity was induced using the phase separation of furfuryl alcohol. These materials have a suite of mesopore and macropore structures, the domains of which can be controlled by adjusting the synthesis conditions. These conditions were studied in detail to optimize the pore interconnectivity, the monolith stability, the pore volume and the surface area.

This work is concerned with the design and synthesis of the cheap, late first row transition metal complexes of Schiff base ligand systems. The prepared complexes readily afford systematic variation in order to probe potency and understand the role of metal, chelating ligands and anionic ligands when carrying out their cytotoxic effect. This study has lead to a better understanding of the action of these classes of complex and will be used to direct the design of new anti-cancer metallopharmaceuticals going forward. This thesis details the synthesis of a library of Schiff base macroacyclic ligands and their novel late first row transition metal complexes with varying anionic counterparts. The creation of a library with several degrees of variability provides a wide array of parameters to afford subtle variation in structure and chemistry e.g. denticity, co-ordination mode, chelate hole size, metal centred redox potentials, hydrolysis rates, co-ordinative saturation, lipophilicity, solubility and more. Complexation of the ligands was carried out by the free ligand and a novel macroacyclic metal template approach using the cheap late first row transition metal salts of Cobalt (II), Nickel (II), Copper (II) and Zinc (II) plus one Ru (III) complex. Structural studies of the 80 generated complexes was carried out by vibrational spectroscopy, elemental analysis, mass spectrometry, magnetic susceptibility and NMR. Single crystal X-ray structures have been determined with 20 reported in this thesis. All ligands act as tridentate ligands in all except one case to form monomeric distorted trigonal-bipyramidal, square-pyramidal or octahedral structures. In the case of zinc nitrate, the ligand L2PhMe acts as a tetradentate ligand to give a distorted octahedral structure. Paramagnetic NMR and solution magnetic susceptibility of paramagnetic complexes was achieved by the Evans NMR method and analysis of the solution NMR showed that L2R and L3R ligands display 2-fold symmetry and are likely either tetradentate in solution or a fast exchange between imine N-donar sites is occurring even down to -65°C. The majority of the resulting complexes of L1R were screened against a panel of three cancer cell lines. Several categories of complex were able to afford structure activity relationships. It was discovered that the ligand is indeed essential for activity of the metal salts against the panel of cell lines and it was largely discovered that the variation in ¿tail group¿ and anionic coordinating ligands played little role in providing a dramatic variation in activity of the metal salt. In general all L1R complexes displayed moderate cytotoxicity showing a trend in activity with respect to the metal in the order RuIII¿CoII>CuII¿ZnII>NiII, over a 6 day exposure to the three cell panel RuIII was shown to be the most potent metal of the L1R series providing IC50 values of 4.6 (0.7) and 7.5 (1.2) ¿M against the DLD-1 and H460 cell lines respectively, which is Ca. 4.6 and 15 iii times less potent than cisplatin to the same cell panel respectively. RuIII was also discovered to be the only metal to provide an IC50 value from a 1 hour exposure to the DLD-1 cell panel. The value of 20.4 (3.5) ¿M is a moderate figure but again Ca. 10 fold less potent than cisplatin for the same test. The L2R and L3R complexes could not be screened by the same comprehension due to their low solubilities. However the lone screen that was possible from the very sparingly soluble complex [CuCl2(L3Bui)] gave the most exciting result and most potent complex of this thesis. After a 6 day exposure, [CuCl2(L3Bui)] gave IC50 values of 4.3 (0.1) and 2.9 (0.1) ¿M against the DLD-1 and H460 cell lines respectively. These values are merely 4 and 6 fold more than Cisplatin to the same cell lines respectively and demonstrates the potential of this class of complex as cytostatic agents. Further studies utilising a semi-quantitative DNA damaging assay, demonstrated that all first row complexes can damage DNA when in the presence of hydrogen peroxide, with the exception of ZnII complexes. CoII appeared to afford the greatest DNA damage with the most intsense bands for double strand breaks and the CuII complex of the ligand L3Bui also demonstrated a greater DNA damage as opposed to its L1Bui analogue.

Gegenstand der vorliegenden Arbeit ist die Herstellung von nanostrukturierten Kohlenstoffen. Die Synthese erfolgt dabei durch die Zwillingspolymerisation der siliziumhaltigen Zwillingsmonomere 2,2’Spirobi[4H-1,3,2-benzodioxasilin] sowie Tetrafurfuryloxysilan. Die entstehenden Nanokomposite werden anschließend carbonisiert und das SiO2-Netzwerk herausgelöst. Die Zwillingsmonomere wurden dabei zunächst templatfrei umgesetzt, um Einflüsse verschiedener Reaktionsparameter auf die Eigenschaften der erhaltenen Kohlenstoffe zu evaluieren. Des Weiteren wurde studiert, wie sich die Zugabe von Hart-Templaten auf das Polymerisationsverhalten der Zwillingsmonomere, sowie die Porosität und Morphologie der daraus resultierenden Kohlenstoffe auswirkt. Für die Charakterisierung der nanostrukturierten Kohlenstoffe wurde vorwiegend auf Elektronenmikroskopie und Stickstoffsorptions-Experimente zurückgegriffen. Mit Hilfe der Zwillingspolymerisation an Hart-Templaten, wie SiO2-Partikeln, Glasfasern und ORMOCER®en konnte die Morphologie, Geometrie, Größe und Porentextur der Kohlenstoffe eingestellt und ein modulares Synthesekonzept für poröse, nanostrukturierte Kohlenstoffe entwickelt werden. Ferner wurden ausgewählte Kohlenstoffe auf Anwendung als Wasserstoffspeicher und Elektrodenmaterial in Lithium-Schwefel-Zellen getestet. In diesem Zusammenhang wurden die Thermogravimetrie, die Differenzkalorimetrie und Stickstoff-Sorptionsmessungen eingesetzt, um die Batterieeigenschaften in Zukunft ohne das Durchführen aufwendiger Zelltests zu prognostizieren.

Gegenstand der vorliegenden Arbeit ist die Herstellung von nanostrukturierten Kohlenstoffen. Die Synthese erfolgt dabei durch die Zwillingspolymerisation der siliziumhaltigen Zwillingsmonomere 2,2’Spirobi[4H-1,3,2-benzodioxasilin] sowie Tetrafurfuryloxysilan. Die entstehenden Nanokomposite werden anschließend carbonisiert und das SiO2-Netzwerk herausgelöst. Die Zwillingsmonomere wurden dabei zunächst templatfrei umgesetzt, um Einflüsse verschiedener Reaktionsparameter auf die Eigenschaften der erhaltenen Kohlenstoffe zu evaluieren. Des Weiteren wurde studiert, wie sich die Zugabe von Hart-Templaten auf das Polymerisationsverhalten der Zwillingsmonomere, sowie die Porosität und Morphologie der daraus resultierenden Kohlenstoffe auswirkt. Für die Charakterisierung der nanostrukturierten Kohlenstoffe wurde vorwiegend auf Elektronenmikroskopie und Stickstoffsorptions-Experimente zurückgegriffen. Mit Hilfe der Zwillingspolymerisation an Hart-Templaten, wie SiO2-Partikeln, Glasfasern und ORMOCER®en konnte die Morphologie, Geometrie, Größe und Porentextur der Kohlenstoffe eingestellt und ein modulares Synthesekonzept für poröse, nanostrukturierte Kohlenstoffe entwickelt werden. Ferner wurden ausgewählte Kohlenstoffe auf Anwendung als Wasserstoffspeicher und Elektrodenmaterial in Lithium-Schwefel-Zellen getestet. In diesem Zusammenhang wurden die Thermogravimetrie, die Differenzkalorimetrie und Stickstoff-Sorptionsmessungen eingesetzt, um die Batterieeigenschaften in Zukunft ohne das Durchführen aufwendiger Zelltests zu prognostizieren.