rdf-syntax-grammar
mods:
  schema location: http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd
  title info:
    title: Structure property relationships for dirhodium antitumor active compounds
    sub title: reactions with biomolecules and in cellulo studies
  name:
    name part: Aguirre Flores, Jessica Dafhne.
    role:
      role term: creator
  name:
    name part: Dunbar, Kim R.
    role:
      role term: thesis advisor.
  type of resource: text
  genre: bibliography
  origin info:
    place:
      place term: txu
    date issued: 2011
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: remote
    extent: 1 online resource.
  abstract: The molecular characteristics that affect the activity of various dirhodium complexes are reported. The importance of the axial position in the action of dirhodium compounds was studied. Three dirhodium complexes with increasing number of accessible axial coordination sites were synthesized and characterized. In cis-[Rh₂([mu]-OAc)₂(np)₂]²+ (np = 1,8- naphthyridine) both axial sites are available for coordination, whereas for cis-[Rh₂([mu]-OAc)₂(np)(pynp)]+² (pynp = 2-(2-pyridyl)1,8-naphthyridine) and cis-[Rh₂([mu]-OAc)₂(pynp)₂]+² the pyridyl arm on the ligand pynp blocks one and two axial sites, respectively. The availability of the axial positions affects the in vitro and in cellulo activity of these complexes demonstrating that open axial coordination sites are necessary for biological activity. The inhibitory activity of derivatives of dirhodium-dppz complexes (dppz = dipyrido[3,2-a:2',3'-c]phenazine) has also been investigated. The dppz derivatives included compounds with electron-withdrawing (Cl, CN, and NO₂) as well as electro-donating (MeO and Me) substituents. These compounds inhibit transcription of T7-RNA polymerase by reducing accessible cysteine residues. The activity correlates with the electron withdrawing character of the substituent on the dppz ligand. Density functional theory (DFT) calculations reveal that the lowest unoccupied molecular orbitals (LUMOs) in the series are ligand-based [pi]* orbitals localized on the phenazine ring. These complexes represent the first family of dirhodium complexes whose inhibitory ability can be tuned by controlling their redox properties. The effect of the presence of diimine ligands in the dirhodium core in both in vitro and in cellulo activity is discussed. The presence of one diimine ligand allows for dual binding, intercalation and covalent, as observed by melting temperature and relative viscosity measurements, as well as electrophoretic mobility shift assay (EMSA). The mono-substituted dirhodium complexes are…
  note: by Jessica D. Aguirre-Flores.
  note: "Major Subject: Chemistry"
  note: Title from author supplied metadata (automated record created 2011-02-28 11:02:00).
  note: Electronic resource.
  note: Doctor of Philosophy Texas A&M University 2009 http://hdl.handle.net/1969.1/ETD-TAMU-2009-12-7614
  note: Includes bibliographical references.
  note: Text (Dissertation)
  subject:
    topic: Major chemistry
  subject:
    topic: Anticancer compounds
  subject:
    topic: Metal-metal bonded complexes
  subject:
    topic: COLO-316 cells
  subject:
    topic: Comet assay
  subject:
    topic: HeLa cells
  subject:
    topic: Dirhodium complexes
  identifier: http://hdl.handle.net/1969.1/ETD-TAMU-2009-12-7614
  record info:
    record content source: TXA
    record creation date: 110304
    record change date: 20151202115611.0
    record identifier: in00002669625