Palladium Complexes of Corroles and Sapphyrins

Palladium complexes of corrole and sapphyrin were prepared in high yield and fully characterized. The corrole provides a tetradentate/trianionic square planar coordination sphere for Pd^II, charge balanced by pyridinium. Both one and two Pd^II ions may be accommodated by the pentapyrrolic skeleton of the sapphyrin, and in each case the macrocycle acts as bidentate/monoanionic ligand and the inner-sphere square planar geometry is completed by allyl anions coordinated in an η³ fashion. NMR spectroscopy and X-ray crystallography data analyses uncovered the presence of interesting stereoisomers due to the flexibility of the ally ligands and also the pyrrole ring(s) that is/are not involved in metal binding.     

Tuning Chemical and Physical Properties of Phosphorus Corroles for Advanced Applications

Although the affinity of metallocorroles to axial ligands is quite low, this is not the case when the chelated element is phosphorus. This work is hence focused on the mechanism of ligand exchange of six-coordinate phosphorus corroles as a tool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor-made modification of photophysical and electrochemical properties. This is exemplified by the facile access to complexes with terminal groups that are of large potential for practical applications based on click chemistry, optical imaging, and surface science.     

Reaction of Lithium Cellulosate with Episulfides

The reactions of propylene, ethylene, and styrene sulfide with cotton fabrics in the form of their lithium cellulosate derivative, obtained by metallation with lithium methoxide, were studied. Both graft and homo-polymerization took place and in the reaction with propylene and ethylene sulfide, cotton fabrics with high polysulfide content were obtained. With propylene sulfide 50% of the monomer polymerized was grafted. The effects of monomer concentration, cellulosate degree of substitution, reaction time, and solvent on the polymerization were investigated. In contrast with propylene and ethylene sulfide, only small conversions were obtained in the reaction with styrene sulfide. The results were attributed to steric effects.     

Adsorption of Silver Nitrate by Cotton Fabrics Containing Polyethylene Sulfide

The adsorption of silver nitrate from aqueous solution by polyethylene sulfide-containing cotton fabrics was investigated. The adsorption could be described by a Freundlich-type isotherm with n= 1. δH^os was calculated from adsorption isotherms and from the equilibrium constant of complex formation and similar results of-5.6 and -5.4 kcal/mole were obtained, respectively. At low silver nitrate concentrations most of the silver nitrate present in solution could be adsorbed. It was found that adsorption by polyethylene sulfide in the fabric was much higher than that of homo-polyethylene sulfide.     

Tempered wave functions: Schrödinger's equation within the light cone

The standard derivation of Schrödinger's equation from a Lorentz-invariant Feynman path integral consists in taking first the limit of infinite speed of light and then the limit of short time slice. In this order of limits the light cone of the path integral disappears, giving rise to an instantaneous spread of the wave function to the entire space. We ascribe the failure of the propagation in time according to Schrödinger's equation to retain the light cone of the path integral to the very nature of the limiting process: it is a regular expansion of a singular approximation problem, because the time-dependent boundary conditions of the path integral on the light cone are lost in this limit. We propose a distinguished limit of the time-sliced relativistic path integral, which produces Schrödinger's equation and preserves the zero boundary conditions on and outside the original light cone of the path integral. This produces an intermediate model between non-relativistic and relativistic mechanics of a single particle quantum particle. These boundary conditions relieve the solutions of Schrödinger's equation in the entire space of several annoying, seemingly unrelated unphysical artifacts, including non-analytic wave functions, spontaneous appearance of discontinuities, non-existence of moments when the initial wave function has a jump discontinuity (e.g., a collapsed wave function after a measurement), and so on. The practical implications of the present formulation are yet to be seen.     

Listing minimal edge-covers of intersecting families with applications to connectivity problems

Let G=(V,E) be a directed/undirected graph, let s,t∈V, and let F be an intersecting family on V (that is, X∩Y,X∪Y∈F for any intersecting X,Y∈F) so that s∈X and t∉X for every X∈F. An edge set I⊆E is an edge-cover of F if for every X∈F there is an edge in I from X to V−X. We show that minimal edge-covers of F can be listed with polynomial delay, provided that, for any I⊆E the minimal member of the residual family F_I of the sets in F not covered by I can be computed in polynomial time. As an application, we show that minimal undirected Steiner networks, and minimal k-connected and k-outconnected spanning subgraphs of a given directed/undirected graph, can be listed in incremental polynomial time.     

Optical technique for classification, recognition and identification of obscured objects

The capability to classify, recognize and to identify objects from spatially low resolution images has high significance in security related applications especially in a case that recognition of camouflaged object is required.In this paper we present a novel approach in which the scenery containing obscured objects which we wish to classify, recognize or identify is illuminated by spatially coherent beam (e.g. laser) and therefore secondary speckles pattern is reflected from the objects. By special image processing algorithm developed for this research and which is basically based upon temporal tracking of the random speckle pattern one may extract the temporal signature of the object. And right after, to use it for its classification (e.g. its separation from the other objects in the scenery), its recognition and identification even in a case that the imager provides poor spatial resolution that by itself does not allow doing the specified detection related operations.