563 research outputs found
Evidence For An Unusual Kinetic Phenomenon In The Metallation Of Porphyrins
Reaction of copper(II) with water soluble porphyrins (Hâporph) in the presence of ethylenediamine shows an unusual and so far unreported kinetic phenomenon that can be explained in terms of supramolecular assembly formation apparently involving all solute species as confirmed via light scattering and conductivity measurements
Effect Of Zinc Cations On The Kinetics Of Supramolecular Assembly And The Chirality Of Porphyrin J-Aggregates
Dilute aqueous solutions of anionic meso-4-sulfonatophenyl-porphyrin (TPPS) extract zinc(ii) ions from glass or quartz surfaces at room temperature and efficiently form the corresponding metal complex (ZnTPPS). The partial or complete formation of ZnTPPS has been probed by UV/Vis spectroscopy and both static and time-resolved fluorescence. The source of zinc(ii) ions has been clearly identified through inductively coupled plasma optical emission spectrometry. The presence of increasing amounts of ZnTPPS slows down the rate of TPPS J-aggregate formation in acid solution. This influences the nucleation step and has a profound impact on the onset of chirality in these species. This evidence indicates the important role of this adventitious metal ion in the interpretation of various spectroscopic and kinetic data for the self-assembly of the TPPS porphyrin and provides some insights into controversial findings on their chirality. The use of this metal derivative as the starting compound for in situ formation of monomeric TPPS is suggested
Mechanism For Copper(II)-Mediated Disaggregation Of A Porphyrin J-Aggregate
J-aggregates of anionic meso-tetrakis(4-sulfonatophenyl)porphyrin form at intermediate pH (2.3â3.1) in the presence of NiSOâ or ZnSOâ (ionic strength, I.S. = 3.2 M). These aggregates convert to monomeric porphyrin units via metallation with copper(II) ions. The kinetics for the disassembly process, as monitored by UV/vis spectroscopy, exhibits zeroth-order behavior. The observed zeroth-order rate constants show a two-term dependence on copper(II) ion concentrations: linear and second order. Also observed is an inverse dependence on hydrogen ion concentration. Activation parameters have been determined for the disassembly process leading to ÎH^â = (+163 ± 15) kJ·molâ»Âč and ÎS^â = (+136 ± 11) J·Kâ»Âč. A mechanism is proposed in which copper(II) cation is in pre-equilibrium with a reactive site at the rim of the J-aggregate. An intermediate copper species is thus formed that eventually leads to the final metallated porphyrin either through an assisted attack of a second metal ion or through a direct insertion of the metal cation into the macrocycle core
A useful form of the recurrence relation between relativistic atomic matrix elements of radial powers
Recently obtained recurrence formulae for relativistic hydrogenic radial
matrix elements are cast in a simpler and perhaps more useful form. This is
achieved with the help of a new relation between the and the
terms ( is a Dirac matrix and are constants) in the
atomic matrix elements.Comment: 7 pages, no figure
Relativistically extended Blanchard recurrence relation for hydrogenic matrix elements
General recurrence relations for arbitrary non-diagonal, radial hydrogenic
matrix elements are derived in Dirac relativistic quantum mechanics. Our
approach is based on a generalization of the second hypervirial method
previously employed in the non-relativistic Schr\"odinger case. A relativistic
version of the Pasternack-Sternheimer relation is thence obtained in the
diagonal (i.e. total angular momentum and parity the same) case, from such
relation an expression for the relativistic virial theorem is deduced. To
contribute to the utility of the relations, explicit expressions for the radial
matrix elements of functions of the form and
---where is a Dirac matrix--- are presented.Comment: 21 pages, to be published in J. Phys. B: At. Mol. Opt. Phys. in Apri
Influence Of DNA On The Rate Of Porphyrin Metallation
Poly(dGâdC)â and poly(dAâdT)â have marked influences on the rate of insertion of copper(II) into cationic porphyrins reflecting the interaction mode of the porphyrin with the nucleic acid
Recurrence relation for relativistic atomic matrix elements
Recurrence formulae for arbitrary hydrogenic radial matrix elements are
obtained in the Dirac form of relativistic quantum mechanics. Our approach is
inspired on the relativistic extension of the second hypervirial method that
has been succesfully employed to deduce an analogous relationship in non
relativistic quantum mechanics. We obtain first the relativistic extension of
the second hypervirial and then the relativistic recurrence relation.
Furthermore, we use such relation to deduce relativistic versions of the
Pasternack-Sternheimer rule and of the virial theorem.Comment: 10 pages, no figure
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