Localization and photodynamic efficacy of two cationic porphyrins varying in charge distributions

Two meso-tetraphenylporphyrin derivatives bearing adjacent: 5,10-di[4-(N-trimethylaminophenyl)-15,20-diphenylporphyrin (DADP-a) or opposite: 5,15-di[4-(N-trimethylaminophenyl)-10,20-diphenylporphyrin (DADP-o) cationic-N-(CH3)3+ groups on two of the para-phenyl positions were examined with regard to photodynamic properties as a function of charge distribution. The two adjacent positive charges in the DADP-a structure result in a molecular distortion (asymmetry), likely from electrostatic repulsion. This could be responsible for the unusual interaction of this compound with some solvents and detergent micelles. In contrast, DADP-o is a much more symmetric molecule. In a cellular environment, fluorescence spectra of the two agents were essentially identical. Subcellular localization played a major role in photodynamic efficacy. DADP-a localized in mitochondria, and irradiation of photosensitized cells (640-650 nm) resulted in a rapid loss of the mitochondrial membrane potential (delta(psi)m), usually a prelude to apoptotic cell death. In contrast, DADP-o localized in lysosomes, and extensive lysosomal photodamage was observed after irradiation. Both steady-state accumulation levels and absorbance spectra favored DADP-o, but the light dose required for a 90% cell kill was two-fold greater for DADP-o than for DADP-a, at a constant extracellular sensitizer concentration. These data indicate that, on a photons/cell basis, DADP-a was five-fold more efficacious. Fluorescence emission spectra in different solvents and detergents demonstrated a tendency for DADP-a association. We interpret these results to indicate partition of both drugs to membrane loci, with mitochondriabeing the more lethal site for photodamage.     

Benzoylbiliverdins from chemical oxidation of dodeca-substituted porphyrins

Oxidation of dodeca-substituted porphyrin 1 in the presence of NaNO2/TFA and air afforded benzoylbiliverdin 3 in 77% yield; under similar conditions the Ni(II)-porphyrin 2 was mainly nitrated at a cyclohexenyl ring; key X-ray structures are presented.     

Influence of low intensity noise on assemblies of diffusively coupled chaotic cells

The effect of time-correlated and white Gaussian noises of low intensity on one-dimensional arrays consisting of diffusively coupled chaotic cells is analyzed. An improvement or worsening of the synchronization between cells of the array driven by low-intensity colored noise is observed for a resonant interval of time correlation values. A comparison between colored and white noise and additive and multiplicative contribution has been carried out investigating the nonlinear cooperative effects of noise strength, correlation time, and coupling strength to control spatiotemporal chaos in coupled arrays of chaotic cells. The possibility to distinguish highly correlated areas of a diffusively coupled network of cells by using low-intensity time correlated noise is discussed. (c) 2001 American Institute of Physics.     

Intrinsic Definitions of “Relative Velocity” in General Relativity

Given two observers, we define the “relative velocity” of one observer with respect to the other in four different ways. All four definitions are given intrinsically, i.e. independently of any coordinate system. Two of them are given in the framework of spacelike simultaneity and, analogously, the other two are given in the framework of observed (lightlike) simultaneity. Properties and physical interpretations are discussed. Finally, we study relations between them in special relativity, and we give some examples in Schwarzschild and Robertson-Walker spacetimes.     

The xraylib library for X-ray–matter interactions. Recent developments

This work presents the recent developments of xraylib, an ANSI C library that provides convenient access to a large number of X-ray related databases, with a focus on quantitative X-ray fluorescence applications. The enhancements include improved X-ray fluorescence production cross sections that take into account cascade effects and M-lines, as well as revised line energies, atomic level widths, Compton broadening profiles etc. A full overview of the complete application programming interface is presented.     

A new concept in lightning parameters measurement

Nowadays the electrical activity measured in tall objects has been widely characterized, but the collected data of lightning rods installed in buildings do not amount to enough to obtain reliable statistics. The measures stored at relatively few points are not representative of the different types of installations. Furthermore, the protection model applied for lightning air terminal installations is based on theoretical models. This paper describes the design of a micro-station to measure some lightning parameters in real lightning air terminal installations correlated to the nature of emplacement instead of triggering lightning or choosing points with a high number of lightning impacts.     

Enzymatic resolution of trans-4-(4'-fluorophenyl)-3-hydroxymethylpiperidines, key intermediates in the synthesis of (-)-Paroxetine.

Two Candida antarctica lipases catalyze the enantioselective acylation of N-substituted trans-4-(4'-fluorophenyl)-3-hydroxymethylpiperidines in organic solvents. These two lipases show opposite stereochemical preference in these processes. Both enantiomers can be obtained in their optically pure forms. The (3S,4R) isomer, is an intermediate for the synthesis of (-)-Paroxetine.     

Pre-emption in resource-constrained project scheduling

The Resource-Constrained Project Scheduling Project (RCPSP), together with some of its extensions, has been widely studied. A fundamental assumption in this basic problem is that activities in progress are non-preemptable. Very little effort has been made to uncover the potential benefits of discrete activity pre-emption, and the papers dealing with this issue have reached the conclusion that it has little effect on project length when constant resource availability levels are defined. In this paper we show how three basic elements of many heuristics for the RCPSP – codification, serial SGS and double justification – can be adapted to deal with interruption. The paper is mainly focussed on problem 1_PRCPSP, a generalization of the RCPSP where a maximum of one interruption per activity is allowed. However, it is also shown how these three elements can be further adapted to deal with more general pre-emptive problems. Computational experiments on the standard j30 and j120 sets support the conclusion that pre-emption does help to decrease project length when compared to the no-interruption case. They also prove the usefulness of the justification in the presence of pre-emption. The justification is a RCPS technique that can be easily incorporated into a wide range of algorithms for the RCPSP, increasing their solution quality – maintaining the number of schedules calculated.