EPR-detected photoinduced electron transfer in three structurally related molecular triads

A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C₆₀, TTF-P-C₆₀ and C-P-P_F, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C₆₀, versus fluorinated free-base porphyrin, P_F), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C₆₀ triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C₆₀: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge.     

Temporary attachment of carbohydrates to cyclopeptide templates: a new strategy for single-bead analysis of multivalent neoglycopeptides

Employing a cleavable carbohydrate–peptide linker, a new strategy for single-bead analysis of multivalent cyclic neoglycopeptides based on Edman degradation is described. Edman degradation of glycopeptides is hampered by the acid lability of the glycosidic bond and potential incompatibilities of phenylthiohydantoin (PTH) derivatives of glycosylated amino acids with PTH derivatives of the proteinogenic amino acids. To overcome this problem, carbohydrates are detached from the cyclopeptide templates before single-bead analysis, allowing for micro sequencing under routine conditions. With this strategy, application of multivalent cyclic neoglycopeptides in split-mix libraries with a subsequent screening process becomes possible for the first time.     

Robust Speed Control of a Low Damped Electromechanical System Based on CRONE Control: Application to a Four Mass Experimental Test Bench

Robust speed control of a low damped electromechanical system with backlash is studied, controlled load angular speed being not measured. The proposed control strategy combines a Luenberger observer (load angular speed and load torque disturbance estimations) and a robust CRONE controller. The observer provides estimation of the load angular speed and of the disturbance torque applied on the load. Through the computation of only three independent parameters (as many as a PID controller), the CRONE controller permits to ensure the robust speed control of the load in spite of plant parametric variations and speed observation errors. The proposed control strategy is applied to a four mass experimental test bench.     

A new insight into the understanding of the collapsed form of poly(N-isopropylacrylamide) molecules

Possible collapsed forms of poly(N-isopropylacrylamide) molecules are reviewed on the basis of first principle calculations. Various configurations and associated conformations are detailed. The calculated optimized structures exhibit different possibilities of creating networks of intra-molecular bonds of the hydrogen type. We show that the most remarkable one is able to form a local, self-saturated and well ordered helix. We also indicate in which direction the synthesis of the molecule should be oriented to improve its global behavior in term of hydrophobic/hydrophilic behavior.     

Algorithmic and explicit determination of the Lovász number for certain circulant graphs

We consider the problem of computing the Lovász theta function for circulant graphs C_n,J of degree four with n vertices and chord length J, 2?J?n. We present an algorithm that takes O(J) operations if J is an odd number, and O(n/J) operations if J is even. On the considered class of graphs our algorithm strongly outperforms the known algorithms for theta function computation. We also provide explicit formulas for the important special cases J=2 and J=3.     

Half-width temperature dependence of nitrogen broadened lines in the ν2 band of H2O

Forty-seven N₂ broadened water vapor line-widths have been measured in the 1845-2140 cm⁻¹ spectral range with a Fourier Transform spectrometer in the 258-330 K temperature range at a spectral resolution of 0.005 cm⁻¹ for the lines with upper state rotational quantum number up to 16. The measured exponents of the temperature dependence of the width exhibit a large range of values from 1.60 to −0.86. Theoretical calculations were made using a semi-empirical technique based on the Anderson theory. The calculated broadening coefficients as well as the temperature exponents for the half-width agree satisfactory with measured values.     

Galactose oxidase immobilized on silica in an analytical determination of galactose-containing carbohydrates.

Galactose oxidase from Fusarium graminearum IMV-1060 adsorbed on, and covalently bound to, silica carriers has been used for analytical determinations of D-galactose and galactose-containing sugars. Using a flowing oxygen electrode of the Clark-type, sensor system for enzymatic analysis of water solutions of galactose-containing carbohydrates was made. Measurements were taken both in the pulse and continuous modes of a substrate flowing through a column with an immobilized biocatalyst. The linear measurement ranges for galactose-containing carbohydrates concentrations were determined.     

Multiplicité des solutions d'équilibre d'une coque de Marguerre–von Kármán membranaireMultiplicity of solutions to the Marguerre–von Kármán membrane equations

We build explicitly an infinite number of equilibrium solutions of unloaded Marguerre–von Kármán membrane shells. This construction is based upon the existence of three elementary solutions, together with the solution of a Monge–Ampère equation associated with a partition of the reference configuration of the shell. To cite this article: A. Léger, B. Miara, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 649–654.     

Study of the spontaneous formation of organic layers on carbon and metal surfaces from diazonium salts

This study investigates the spontaneous grafting of different para-substituted phenyl groups on carbon and metallic surfaces from diazonium salts solutions. Glassy carbon, nickel, zinc and iron plates were allowed to react with an acetonitrile solution of aryldiazonium tetrafluoroborate salt by simple dipping. The surfaces were characterized before and after their immersion by XPS and AFM to evidence the formation of a coating on the different materials. The results are indicative of the presence of substituted phenyl groups on all the investigated surfaces. This study also aims at correlating grafting efficiency with metal reactivities and diazonium salt electronic properties by means of AFM and FT-IRRAS. For this purpose, zinc and nickel were chosen due to their opposite reducing properties and two diazonium salts were selected with electron-donor or -withdrawing para-substituents. The results tend to indicate that redox properties of both partners (diazonium + metal) are of prime importance for grafting to occur.     

Indecomposable modules over the Virasoro Lie algebra and a conjecture of V. Kac

We consider a class of indecomposable modules over the Virasoro Lie algebra that we call bounded admissible modules. We get results concerning the center and the dimensions of the weight spaces. We prove that these modules always contain a submodule with one-dimensional weight spaces. From this follows the proof of a conjecture of V. Kac concerning the classification of simple admissible modules.Preprint Université de Bourgogne-mai 1990