Enhanced acidity, photophysical properties and liposome binding of perfluoroalkylated phthalocyanines lacking C-H bonds

The acid-base, spectroscopic, photophysical and liposome-binding properties of the recently synthesized free base, 29H,31H,1,4,8,11,15,18,22,25-octafluoro-2,3,9,10,16,17,23, 24-octakisperfluoro(isopropyl) phthalocyanine, F64PcH2, are reported. The perfluoroalkylation of the phthalocyanine core renders the hydrogen atoms acidic, with a pK(a) = 6. The F64Pc(-2) dianion is detected already at pH 3, by singular-value decomposition analysis of electronic spectra. F64Pc(-2) generates 1O2 with quantum yields phi(delta) = 0.252 (in MeOH) and 0.019 in liposomes. Metallation of the Pc macrocycle to yield F64PcZn increases phi(delta) to 0.606 and 0.126 in MeOH and liposomes, respectively. Surprisingly, F64Pc(-2) (but not F64PcH2 or F64PcZn) binds strongly to liposomes, with a binding constant K(b) = 25 (mg/mL)(-1). The fully protonated F64PcH2, but not the zwitterionic F64Pc(-2), might favor hydrogen bonding, thus reducing its lipophilicity. Similarly, the Lewis acidity of Zn in F64PcZn, and thus its ability to bind water within a hydrophobic perfluoroalkyl pocket, is significantly enhanced by the fluorinated substituents.     

Electronic structure of the [MNH2]+ (M = Sc-Cu) complexes

B3LYP geometry optimizations for the [MNH2]+ complexes of the first-row transition metal cations (Sc+-Cu+) were performed. Without any exception the ground states of these unsaturated amide complexes were calculated to possess planar geometries. CASPT2 binding energies that were corrected for zero-point energies and including relativistic effects show a qualitative trend across the series that closely resembles the experimental observations. The electronic structures for the complexes of the early and middle transition metal cations (Sc+-Co+) differ from the electronic structures derived for the complexes of the late transition metal cations (Ni+ and Cu+). For the former complexes the relative higher position of the 3d orbitals above the singly occupied 2p(pi) HOMO of the uncoordinated NH2 induces an electron transfer from the 3d shell to 2p(pi). The stabilization of the 3d orbitals from the left to the right along the first-row transition metal series causes these orbitals to become situated below the HOMO of the NH2 ligand for Ni+ and Cu+, preventing a transfer from occurring in the [MNH2]+ complexes of these metal cations. Analysis of the low-lying states of the amide complexes revealed a rather unique characteristic of their electronic structures that was found across the entire series. Rather exceptionally for the whole of chemistry, pi-type interactions were calculated to be stronger than the corresponding sigma-type interactions. The origin of this extraordinary behavior can be ascribed to the low-lying sp2 lone pair orbital of the NH2 ligand with respect to the 3d level.     

Spectroscopic Characterization of a Lead–Lead Dioxide Automobile Battery

Here we combine small angle neutron scattering measurements (SANS) with X-ray diffraction analysis (XRD) and infrared spectroscopy (IR) measurements to obtain information about nanoparticles formed in a series of lead-lead dioxide samples mixed with various CuO concentrations. New vitreous systems with the xCuO???(100?x)[4PbO₂???Pb] composition where x?=?0, 30, and 70?mol% CuO were prepared by the melt-quenching method using CuO mixed in suitable proportion with the active electrodes of a disassembled car battery as the starting materials. The X-ray diffraction patterns permit the identification of the metallic Pb phase and the presence of oxidic nanoparticles of the lead and copper ions. By doping with higher CuO contents, the SANS curves have a concave shape indicating inhomogeneities and tendency of phase separation due to formation of nanoparticles of the lead and copper ions in recycled host matrix. The studied samples can be considered as polydispersed systems. The matrix is the solvent and the soluble phase is formed from the oxidic lead and/or copper particles with sizes smaller than 69?Å dispersed either inside the host matrix grains or between the host matrix grains. The formation of the nanoparticles in the host matrix and the knowledge of the type of nanoparticles have a decisive role in applications for the construction of essential components of the automobile batteries.     

ZnSe‐based conductive nanotemplates for nanofabrication

We show that anodic etching of n‐type ZnSe crystalline substrates leads to the formation of pores which, after nucleation at surface defects, prove to follow the current lines, exhibiting multiplication until the front of the porous network covers the whole available space. No growth of crystallographically oriented pores has been observed in ZnSe. The formation of multilayer porous structures is realized, including layers subjected to successive porosification at two different length scales. The electrochemical pulsed deposition of arrays of Pt nanotubes in the porous ZnSe matrix is demonstrated. The obtained results show that porous ZnSe structures are promising for use as conductive and optically transparent nanotemplates for nanofabrication, in particular for the important application of metal nanotubes. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectral density analysis of the chiral transition in nf=4 finite temperature QCD

We apply the spectral density reweighting technique to the analysis of the chiral phase transition in finite-temperature lattice quantum chromodynamics (QCD) with four flavors of dynamical staggered fermions and m_qa=0.025. Our simulations were performed using the hybrid Monte Carlo method for L_tL³ lattices with L_t=4 and L=6, 8 and 10. We calculate partition function zeros, as well as the maxima of the specific heat and of the susceptibilities for the Polyakov loop and for the chiral condensate. A finite size scaling analysis of these data leads to preliminary results for the critical coupling β_c, for the critical exponent ν, for the latent heat, and for the jumps in the Polyakov loop and in the chiral condensate.     

Periodic solutions for second order differential inclusions with the scalar p-Laplacian

We study periodic problems driven by the scalar p-Laplacian with a multivalued right-hand side nonlinearity. We prove two existence theorems. In the first, we assume nonuniform nonresonance conditions between two successive eigenvalues of the negative p-Laplacian with periodic boundary conditions. In the second, we employ certain Landesman-Lazer type conditions. Our approach is based on degree theory.     

Sur la limite adiabatique des fonctions êta et zêtaOn the adiabatic limit of the eta and zeta functions

In this Note we prove the existence of the adiabatic limit of the η(s) function of an operator on the total space of a fibration over S¹, constructed from an invertible family of first-order differential operators. We identify this limit as the holonomy of a meromorphic family of connections in the trivial bundle. In the same context, the ζ function diverges. We give a formula for the first two terms of the asymptotic expansion. The first result remains true for a non-invertible family if we restrict ourselves to s=0. For a family of Dirac operators, we retrieve the holonomy formula of Bismut–Freed. To cite this article: S. Moroianu, C. R. Acad. Sci. Paris, Ser. I 334 (2002) 131–134     

On the radius of injectivity of null hypersurfaces

We investigate the regularity of past (future) boundaries of points in regular, Einstein vacuum spacetimes. We provide conditions, expressed in terms of a space-like foliation and which imply, in particular, uniform bounds for the curvature tensor, sufficient to ensure the local nondegeneracy of these boundaries. More precisely we provide a uniform lower bound on the radius of injectivity of the null boundaries of the causal past (future) sets . Such lower bounds are essential in understanding the causal structure and the related propagation properties of solutions to the Einstein equations. They are particularly important in construction of an effective Kirchoff-Sobolev type parametrix for solutions of wave equations on . Such parametrices are used by the authors in a forthcoming paper to prove a large data break-down criterion for solutions of the Einstein vacuum equations.

     

The Effect of Functional Groups on the Phase Behavior of Carbon Dioxide Binaries and Their Role in CCS

In recent years we have focused our efforts on investigating various binary mixtures containing carbon dioxide to find the best candidate for CO₂ capture and, therefore, for applications in the field of CCS and CCUS technologies. Continuing this project, the present study investigates the phase behavior of three binary systems containing carbon dioxide and different oxygenated compounds. Two thermodynamic models are examined for their ability to predict the phase behavior of these systems. The selected models are the well-known Peng–Robinson (PR) equation of state and the General Equation of State (GEOS), which is a generalization for all cubic equations of state with two, three, and four parameters, coupled with classical van der Waals mixing rules (two-parameter conventional mixing rule, 2PCMR). The carbon dioxide + ethyl acetate, carbon dioxide + 1,4-dioxane, and carbon dioxide + 1,2-dimethoxyethane binary systems were analyzed based on GEOS and PR equation of state models. The modeling approach is entirely predictive. Previously, it was proved that this approach was successful for members of the same homologous series. Unique sets of binary interaction parameters for each equation of state, determined for the carbon dioxide + 2-butanol binary model system, based on k₁₂–l₁₂ method, were used to examine the three systems. It was shown that the models predict that CO₂ solubility in the three substances increases globally in the order 1,4-dioxane, 1,2-dimethoxyethane, and ethyl acetate. CO₂ solubility in 1,2-dimethoxyethane, 1.4-dioxane, and ethyl acetate reduces with increasing temperature for the same pressure, and increases with lowering temperature for the same pressure, indicating a physical dissolving process of CO₂ in all three substances. However, CO₂ solubility for the carbon dioxide + ether systems (1,4-dioxane, 1,2-dimethoxyethane) is better at low temperatures and pressures, and decreases with increasing pressures, leading to higher critical points for the mixtures. By contrast, the solubility of ethyl acetate in carbon dioxide is less dependent on temperatures and pressures, and the mixture has lower pressures critical points. In other words, the ethers offer better solubilization at low pressures; however, the ester has better overall miscibility in terms of lower critical pressures. Among the binary systems investigated, the 1,2-dimethoxyethane is the best solvent for CO₂ absorption.