85135-24-6Relevant articles and documents
Molecular containers based on amphiphilic PS-b-PMVE dendrigraft copolymers: Topology, organization, and aqueous solution properties
Schappacher, Michel,Putaux, Jean Luc,Lefebvre, Christelle,Deffieux, Alain
, p. 2990 - 2998 (2005)
The synthesis, characteristics, and properties of amphipatic, water-soluble dendrigrafts, with a polystyrene core and polystyrene-b-poly(methyl vinyl ether) (PS-b-PMVE) diblock as external branches, are described. The dendrigrafts are observed by AFM and TEM as egglike or long cylindrical objects which can self-organize intramolecularly in segregated subdomains forming flowerlike or strings of flowerlike objects. In organic solvents the dendrigrafts behave as fully soluble isolated macromolecules and show in water a low critical solubility temperature (LCST) at t > 30°C. The ability of the amphiphilic PS-b-PMVE dendrigrafts to complex and transport in water organic (pyrene) and metallo-organic (manganese tetraphenyl porphyrin) molecules is investigated. The possibility to stabilize the high oxidation state of metallo-porphyrin complexes through their encapsulation into the dendrigraft is shown.
Study of (Tetraphenylporphinato)manganese(III)-Catalyzed Epoxidation and Demethylation Using p-Cyano-N,N-dimethylaniline N-Oxide as Oxygen Donor in a Homogeneous System. Kinetics, Radiochemical Ligation Studies, and Reaction Mechanism for a Model of Cytochrome P-450
Powell, Michael F.,Pai, Emil F.,Bruice, Thomas C.
, p. 3277 - 3285 (2007/10/02)
Oxygen transfer from p-cyanodimethylaniline (p-CNDMANO) to cyclohexene as well as "intramolecular" oxygen transfer accompained by demethylation to yield p-cyanomonomethylaniline (p-CNMMA) are strongly catalyzed by ligated (tetraphenylporphinato)MnIII (i.e., XMnIIITPP).These reactions have been studied in dry, oxygen-free benzonitrile.Radiochemical studies show that H2O (or TOH) is not bound to XMnIIITPP in aprotic solvents so that the MnIII moiety is pentacoordinate.Oxygen transfer occurs through the reversible formation of the hexacoordinated species p-CNDMANO*MnIII(X)TPP.This species decomposes to p-cyanodimethylaniline (p-CNDMA) + O=MnV(X)TPP.Reactions of cyclohexene with O=MnV(X)TPP yields cyclohexene epoxide and XMnIIITPP whereas p-CNMMA is formed directly from the p-CNDMANO*MnIII(X)TPP complex.The rates of product formation are shown to be dependent upon the nature of the ligand (X- = F-, Cl-, Br-, I-, OCN-).In the absence of the axial ligand X-, the rates of reaction are extremely slow.Thus, the MnIII C2-cap-porphyrin (XMnIIICAPTPP), which can only form an O=MnV porphyrin species wherein the Mn moiety is not complexed to X- as a sixth ligand, shows almost no tendency to act as a catalyst for oxygen transfer.The necessary presence of the axial ligand X- and the dependence of rate upon X- requires the structure of the oxygen transfer species to be quivalent to O=MnV(X)TPP.A kinetic analysis is presented (Scheme III) which has allowed the determination of the influence of the ligands X- upon the various rate constants (Table IV) involved in the overall oxidations.By employing p-CNDMANO as oxygen donor, multiple catalytic turnovers without loss of porphyrin have been realized.
