BIOLOGICAL ACTIVITIES OF PHTHALOCYANINES—IV. TYPE II SENSITIZED PHOTOOXIDATION OF L-TRYPTOPHAN AND CHOLESTEROL BY SULFONATED METALLO PHTHALOCYANINES

Abstract— Sulfonated phthalocyanine and a series of its metal chelates in combination with red light irradiation led to the degradation of L-tryptophan in oxygenated aqueous solution. The photoproducts and the rate of transformation of L-tryptophan are compared with hematoporphyrin and rose bengal sensitized photooxidation. In all cases the primary photoproducts are characterized as cis and trans -3a-hydroperoxy-l,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid. Support for the involvement of singlet excited oxygen is obtained from azide inhibition and the formation of the specific singlet oxygen product with cholesterol. We observed the contribution of another pathway in the case of the manganese complex.     

Controlling Selectivity in Plasmonic Catalysis: Switching Reaction Pathway from Hydrogenation to Homocoupling Under Visible-Light Irradiation

Plasmonic catalysis enables the use of light to accelerate molecular transformations. Its application to the control reaction selectivity is highly attractive but remains challenging. Here, we have found that the plasmonic properties in AgPd nanoparticles allowed different reaction pathways for tunable product formation under visible-light irradiation. By employing the hydrogenation of phenylacetylene as a model transformation, we demonstrate that visible-light irradiation can be employed to steer the reaction pathway from hydrogenation to homocoupling. Our data showed that the decrease in the concentration of H species at the surface due to plasmon-enhanced H₂ desorption led to the control in selectivity. These results provide important insights into the understanding of reaction selectivity with light, paving the way for the application of plasmonic catalysis to the synthesis of 1,3-diynes, and bringing the vision of light-driven transformations with target selectivity one step closer to reality.     

Effect of filter type on the statistics of energy transfer between resolved and subfilter scales from a-priori analysis of direct numerical simulations of isotropic turbulence

The effects of different filtering strategies on the statistical properties of the resolved-to-subfilter scale (SFS) energy transfer are analysed in forced homogeneous and isotropic turbulence. We carry out a-priori analyses of the statistical characteristics of SFS energy transfer by filtering data obtained from direct numerical simulations with up to 2048³ grid points as a function of the filter cutoff scale. In order to quantify the dependence of extreme events and anomalous scaling on the filter, we compare a sharp Fourier Galerkin projector, a Gaussian filter and a novel class of Galerkin projectors with non-sharp spectral filter profiles. Of interest is the importance of Galilean invariance and we confirm that local SFS energy transfer displays intermittency scaling in both skewness and flatness as a function of the cutoff scale. Furthermore, we quantify the robustness of scaling as a function of the filtering type.     

Practical aspects of computational chemistry calculations through PC networks: the RAMSES–Beowulf implementation

We have built clusters of PC using up to 320 processors in parallel. The first cluster was built in 1996 from 64 computers. The parallel architectures are named RAMSES. In this article, we share our experience and discuss our choices. The architecture is composed of Pentium processors connected by a 100 Mbits/s Ethernet network. Because RAMSES are built of independent computers, the system is easily maintained, and can be modified by adding or removing machines. Two programs, which are dedicated to molecular modeling and were previously developed on single machines (OSIRIS and IMPALA), have been adapted. IMPALA models peptide and protein interaction with membranes, OSIRIS simulates an ab initio folding of globular proteins. After parallelization, each program consists of two parts: one is the human/RAMSES interface, and the second is the simulation per se. The parallel architecture is transparent for the users. Tests of the IMPALA and OSIRIS efficiencies are shown and discussed. © 2000 John Wiley & Sons, Inc. J Comput Chem 22: 172–177, 2001     

Kinematics and dynamics of small-scale vorticity and strain-rate structures in the transition from isotropic to shear turbulence

We applied a technique that defines and extracts “structures” from a DNS dataset of a turbulence variable in a way that allows concurrent quantitative and visual analysis. Local topological and statistical measures of enstrophy and strain-rate structures were compared with global statistics to determine the role of mean shear in the dynamical interactions between fluctuating vorticity and strain-rate during transition from isotropic to shear-dominated turbulence. We find that mean shear adjusts the alignment of fluctuating vorticity, fluctuating strain-rate in principal axes, and mean strain-rate in a way that (1) enhances both global and local alignments between vorticity and the second eigenvector of fluctuating strain-rate, (2) two-dimensionalizes fluctuating strain-rate, and (3) aligns the compressional components of fluctuating and mean strain-rate. Shear causes amalgamation of enstrophy and strain-rate structures, and suppresses the existence of strain-rate structures in low-vorticity regions between enstrophy structures. A primary effect of shear is to enhance “passive” strain-rate fluctuations, strain-rate kinematically induced by local vorticity concentrations with negligible enstrophy production, relative to “active,” or vorticity-generating strain-rate fluctuations. Enstrophy structures separate into “active” and “passive” based on the level of the second eigenvalue of fluctuating strain-rate. We embedded the structure-extraction algorithm into an interactive visualization-based analysis system from which the time evolution of a shear-induced hairpin enstrophy structure was visually and quantitatively analyzed. The structure originated in the initial isotropic state as a vortex sheet, evolved into a vortex tube during a transitional period, and developed into a well-defined horseshoe vortex in the shear-dominated asymptotic state.     

Structural investigation of reconstituted high density lipoproteins by scanning tunnelling microscopy

Being able to participate in the reverse cholesterol transport (RCT), high density lipoproteins (HDL) are known to be anti-atherogenic. In order to understand such a process, it is thus essential to have a detailed knowledge of the structure and molecular organisation of HDL.

Reconstituted nascent high density lipoproteins (r-HDL), consisting of synthetic phospholipids together with different apolipoproteins (apo A-I, A-IV and E), were thus analysed by scanning tunnelling microscopy (STM).

Both shape and dimensions of the discoidal HDL particles measured by this technique were found in good agreement with the data available from the literature.

The accuracy of the STM pictures presented in this paper enables for the first time the visualisation of the molecular organisation of such macromolecules. The arrangement of the protein as antiparallel helical segments, is consistent with the general mode of organisation of apolipoprotein/phospholipid discoidal particles previously reported.     

Development of a mobile system based on laser-induced breakdown spectroscopy and dedicated to in situ analysis of polluted soils

Principal Components Analysis (PCA) is successfully applied to the full laser-induced breakdown spectroscopy (LIBS) spectra of soil samples, defining classes according to the concentrations of the major elements. The large variability of the LIBS data is related to the heterogeneity of the samples and the representativeness of the data is finally discussed.     

Biological activities of phthalocyanines--III. Photoinactivation of V-79 Chinese hamster cells by tetrasulfophthalocyanines

Abstract— Tetrasulfophthalocyanine and a series of its metal chelates were tested for their ability to photoinactivate V-79 Chinese hamster cells. Incubation of cells for 1 h with tetrasulfophthalocyanine at 5 μM effectively sensitized cells towards red light. At the 1% survival level, the dye was 4 x more efficient than hematoporphyrin, efficiency being defined in terms of drug concentration in the medium and incident light fluence rather than on the basis of quanta absorbed. Chelation of the dye with metal ions resulted in most cases in a greatly diminished photosensitizing effect, except for cerium. The cerium complex was about 5 x more effective for cell killing than the metal free tetrasulfophthalocyanine and 20 x more efficient as compared to hematoporphyrin. Hypoxic conditions resulted in total loss of photoactivity indicating the involvement of oxygen in the action mechanism. The inactivation by near-UV light by these drugs was also investigated. The potential of sulfonated phthalocyanines as novel photosensitizers for photodynamic cancer therapy is discussed.     

BIOLOGICAL ACTIVITIES OF PHTHALOCYANINES—VI. PHOTOOXIDATION OF L-TRYPTOPHAN BY SELECTIVELY SULFONATED GALLIUM PHTHALOCYANINES: SINGLET OXYGEN YIELDS AND EFFECT OF AGGREGATION

Abstract— The photosensitized oxidation of L-tryptophan by gallium phthalocyanines sulfonated to different degrees is studied as a function of both substrate and sensitizer concentrations in water and 50% MeOH-H₂O solutions. The maximum quantum yield of singlet oxygen was found to be nearly 0.5 for all sulfonated gallium complexes. The effect of adding sulfonate groups in the phthalocyanine backbone is to change the tendency of dye molecules to dimerize or aggregate in a particular solvent. A shift in the chemical equilibrium away from the monomeric state, which occurs at high dye concentrations and at lower degrees of dye sulfonation, results in a reduced photochemical yield. The variation of quantum yields in different solvent systems and at several wavelengths is similarly accounted for by the fraction of light absorbed by the productive monomer state.     

BIOLOGICAL ACTIVITIES OF PHTHALOCYANINES–VII. PHOTOINACTIVATION OF V-79 CHINESE HAMSTER CELLS BY SELECTIVELY SULFONATED GALLIUM PHTHALOCYANINES

Abstract Gallium chloride phthalocyanines sulfonated to different degrees were tested for their ability to inactivate V-79 Chinese hamster cells in the presence of red light. The mono- and disulfonated compounds were the most active whereas the tri- and tetrasulfonated complexes were completely void of photoactivity. In addition, large variations in photoactivity were observed among the four isomeric disulfonated derivatives with the most hydrophobic isomer exhibiting the highest photoactivity. Prolonged exposure to the disulfonated complex resulted in increased photosensitization. Complexing the dye with Al instead of Ga resulted in a slightly increased photosensitizing effect.