Nano-urchin: The formation and structure of high-density spherical clusters of vanadium oxide nanotubes

We report the observation of urchin-like nanostructures consisting of high-density spherical nanotube radial arrays of vanadium oxide nanocomposite, successfully synthesized by a simple chemical route using an ethanolic solution of vanadium tri-isopropoxide and alkyl amine hexadecylamine for 7 days at 180oC. The results show that the growth process of the NanoUrchin occurs in stages, starting with a radial self-organized arrangement of lamina followed by the rolling of the lamina into nanotubes. The longest nanotubes are measured to be several micrometers in length with diameters of ~120 nm and hollow centers typically measured to be ~75 nm. The NanoUrchin have an estimated density of nanotubes of ~40 sr-1. The tube walls comprise layers of vanadium oxide with the organic surfactant intercalated between atomic layers. The interlayer distance is measured to be 2.9 ± 0.1 nm and electron diffraction identified the vanadate phase in the VOx nanocomposite as orthorhombic V2O5. These nanostructures may be used as three-dimensional composite materials and as supports for other materials.

Access to modified geiparvarins using Pd(0)-mediated C-C bond forming reactions

Geiparvarin is a natural product which contains both a 3(2H)-furanone and a coumarin moiety in its structure. The aim of this project was to investigate the use of Pd(0)-mediated C–C bondforming reactions to produce structurally modified geiparvarins. Chapter 1 consists of a review of the relevant literature, including that pertaining to the syntheses of selected naturally occurring 3(2H)-furanones. The known syntheses of geiparvarin and closely related analogues are examined, along with the documented biological activity of these compounds. The synthetic routes which allow access to 4-substituted-3(2H)-furanones are also described. Chapter 2 describes in detail the synthesis of a variety of novel structurally modified geiparvarins by two complementary routes, both approaches utilising Pd(0)-mediated crosscoupling reactions, and discusses the characterisation of these compounds. The preparation of 5-ethyl-3(2H)-furanones is described, as is their incorporation into geiparvarin and the corresponding 5″-alkylgeiparvarin analogues via formation and dehydration of intermediate alcohols. Halogenation of 5-ethyl-3(2H)-furanones and the corresponding geiparvarin derivatives is discussed, along with further reactions of the resulting halides. Preparation of 3″-arylgeiparvarins involving both Suzuki–Miyura and Stille reactions, using the appropriate intermediate iodides and bromides, is described. The application of Stille and Heck conditions to give 3″-ethenylgeiparvarin analogues and Sonogashira conditions to produce 3″-ethynylgeiparvarin analogues, using the relevant intermediate iodides, is also extensively outlined. Chapter 3 contains all of the experimental data and details of the synthetic methods employed for the compounds prepared during the course of this research. All novel compounds prepared were fully characterised using NMR spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis; the details of which are included.

Atomic layer structure of vanadium oxide nanotubes grown on nanourchin structures

We report the detailed characterization of high quality vanadium oxide (VOx) nanotubes (NTs) and highlight the zipping of adjacent vanadate layers in such NTs formed on remarkable nanourchin structures. These nanostructures consist of high-density spherical radial arrays of NTs. The results evidence vanadate NTs with unprecedented uniformity and evidences the first report of vanadate atomic layer zipping. The NTs are ∼2 μm in length with inner diameters of 20-30 nm. The tube walls comprise scrolled triplet-layers of vanadate intercalated with organic surfactant. Such high-volume structures might be useful as open-access electrolyte scaffolds for lithium insertion-based charge storage devices.