Photodynamics of the bacteriochlorophyll-carotenoid system. 2. Influence of central metal,solvent and beta-carotene on photobleaching of bacteriochlorophyll derivatives

Bacteriochlorophyll (BChl) derivatives (with central Mg replaced by metal "M") ([M]-BChl with M = 2H, Mg, Zn, Pd, Cu) have been investigated for their photodynamic capacity and stability toward photodegradation in organic solvents and aqueous micellar solution. A protocol has been developed for screening new sensitizers. BChl and [Zn]-BChl are efficient sensitizers, but they are also quickly degraded by the reactive oxygen species (ROS) produced by autosensitization, as well as by hetero-sensitization with 17(4)-methyl-13(2)-demethoxycarbonyl-pheophorbide a (MPP). Photostable [Cu]-BChl is a poor sensitizer, whereas [Pd]-BChl and bacteriopheophytin a are not only very efficient sensitizers but are also very stable toward ROS. beta-Carotene is no efficient physical quencher of ROS in the system; rather, it acts as a photochemical quencher that competes with [M]-BChl and undergoes photooxygenation at high rates. Photolability seems to depend on the pigment oxidation potential and, in parallel, on the presence of central metals preferring coordination numbers higher than 4, whereas photodynamic capacity depends on long excited state life-times of the pigment or efficient intersystem crossing (or both).     

Noncommutative Dynamics of Random Operators

We continue our program of unifying general relativity and quantum mechanics in terms of a noncommutative algebra А on a transformation groupoid Γ = E × G where E is the total space of a principal fibre bundle over spacetime, and G a suitable group acting on Γ . We show that every a ∊ А defines a random operator, and we study the dynamics of such operators. In the noncommutative regime, there is no usual time but, on the strength of the Tomita–Takesaki theorem, there exists a one-parameter group of automorphisms of the algebra А which can be used to define a state dependent dynamics; i.e., the pair (А, ϕ), where ϕ is a state on А, is a “dynamic object.” Only if certain additional conditions are satisfied, the Connes–Nikodym–Radon theorem can be applied and the dependence on ϕ disappears. In these cases, the usual unitary quantum mechanical evolution is recovered. We also notice that the same pair (А, ϕ) defines the so-called free probability calculus, as developed by Voiculescu and others, with the state ϕ playing the role of the noncommutative probability measure. This shows that in the noncommutative regime dynamics and probability are unified. This also explains probabilistic properties of the usual quantum mechanics.     

Entropy Numbers of Trudinger-Strichartz Embeddings of Radial Besov Spaces and Applications

The asymptotic behaviour of entropy numbers of Trudinger–Strichartzembeddings of radial Besov spaces on Rⁿ into exponential Orliczspaces is calculated. Estimates of the entropy numbers as wellas estimates of entropy numbers of Sobolev embeddings of radialBesov spaces are applied to spectral theory of certain pseudo-differentialoperators.     

Solubility of Lanthanide Chlorides ( Ln Cl3) in Alkali Metal Chlorides ( M Cl): Thermodynamics and Electrical Conductivity of the M 3 Ln Cl6 Compounds

Summary.  Several compounds may exist in LnCl₃–MCl mixtures. Those corresponding to the M ₂ LnCl₅ and MLn ₂Cl₇ stoichiometries are formed in a few systems only, with diverse stability strongly dependent on both the corresponding lanthanide and alkali metal. On the other hand, M ₃ LnCl₆ that occur in most systems have a far larger stability range and melt congruently. These latter compounds were investigated in the present work by differential scanning calorimetry and electrical conductivity measurements. The thermodynamic and transport properties were correlated to structural features and related to the mechanism of compound formation. Corresponding author. E-mail: Marcelle.Gaune-Escard@polytech.univ-mrs.fr Received October 2, 2002; accepted November 6, 2002 Published online April 24, 2003 RID="a" ID="a" This paper is dedicated to Professor H. Gamsj?ger on the occasion of his birthday     

A nonsmooth Lyapunov function and stability for ODE’s of Caratheodory type

The problem of Lyapunov stability for systems of ODE’s of Caratheodory type is considered. It is proved that without the necessity of calculating Dini or Clarke generalized gradients, the locally Lipschitz Lyapunov function can follow different kinds of stability.     

Penalization methods for reflecting stochastic differential equations with jumps

The problem of approximation of a solution to a reflecting stochastic differential equation (SDE) with jumps by a sequence of solutions to SDEs with penalization terms is considered. The approximating sequence is not relatively compact in the Skorokhod topology J ¹ and so the methods of approximation based on the J ¹-topology break down. In the paper, we prove our convergence results in the S-topology on the Skorokhod space D(R⁺,?R ^d ) introduced recently by Jakubowski. The S-topology is weaker than J ¹ but stronger than the Meyer-Zheng topology and shares many useful properties with J ¹.     

Analysis of the normal modes of molecules with D3h symmetry: Infrared spectra of monomeric s-triazine and cyanuric acid

Normal modes of s-triazine and cyanuric acid were calculated at the DFT(B3LYP)/6-311++G(d,p) level. These modes were analyzed in terms of potential energy distribution (PED), computed using a specially designed set of symmetry coordinates. The normal-mode analysis was described in detail and the PED matrix definition used in the calculations was provided. Particular attention has been devoted to the degenerate vibrations. The experimental infrared spectra of s-triazine and cyanuric acid isolated in low-temperature Ar matrices have been recorded and interpreted by comparison with the theoretically predicted normal modes. In the spectrum of matrix-isolated s-triazine, the IR bands originating from ¹³C and ¹⁵N isotopologues with one of the ring atoms substituted by a rare isotope were detected. These bands were identified thanks to the excellent agreement between the experimentally observed and theoretically predicted isotope shifts.     

A synthetic approach to the functionalized hydroazulene core of guanacastepenes and heptemerenes

A functionalized hydroazulene derivative has been synthesized efficiently from 2-methylcyclopent-2-en-1-one as a part of a study oriented toward the total synthesis of diterpenoids of biological significance, guanacastepenes, and heptemerones.     

A convenient synthesis of deuterium labeled tertiary aliphatic nitro ketones and nitriles - starting materials for preparation of deuterated cyclic nitrones, isomeric hydroxylamines, and corresponding C-nitroso compounds

Tertiary aliphatic β- and γ-nitro nitriles and ketones deuterated in (several) selected positions had been synthesized. The deuterated nitro compounds served as a starting material for the corresponding deuterium labeled nitrones or hydroxylamines (reducing with aluminum amalgam). Further oxidation of the last two groups of compounds with sodium periodate or m-CPBA afforded the relevant deuterated tertiary C-nitroso compounds.