Evidence For An Unusual Kinetic Phenomenon In The Metallation Of Porphyrins

Reaction of copper(II) with water soluble porphyrins (H₂porph) 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 (2.3–3.1) in the presence of NiSO₄ or ZnSO₄ (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 ΔH^≠ = (+163 ± 15) kJ·mol⁻¹ and ΔS^≠ = (+136 ± 11) J·K⁻¹. 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 $r^a$ and the $\beta r^b$ terms ($\beta$ is a $4\times 4$ Dirac matrix and $a, b$ 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 $r^\lambda$ and $\beta r^\lambda$ ---where $\beta$ 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(dG–dC)₂ and poly(dA–dT)₂ 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