Preparation and characterization of 1,2,3‐triazole‐cured polymers from endcapped azides and alkynes

Fourteen commercial polyols have been characterized by GPC, NMR spectroscopy, and elemental analysis. From these, eight corresponding tosylates, six nitrate esters, seven mesylates, 13 alkynes, and 14 azides have been prepared and all these derivatives have been fully characterized. Five alkyne monomers and eight azide monomers were also prepared. Twelve alkynes and 13 azides (functionality 2–4) were combined in 1,3‐dipolar cycloaddition reactions under neat conditions to prepare triazole‐cured polymers, avoiding any heavy metal catalyst. Characterization by NMR spectroscopy, elemental analysis, and gel permeation chromatography indicated triazole polymers 14 , 22 , 23 , 28 , and 30 with degrees of polymerization of 17–28 to be the best candidates for future work. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 238–256, 2008     

Use of diagnostic neutral losses for structural information on unknown aromatic metabolites: an experimental and theoretical study

This work presents the use of neutral losses (NL) for the identification of compounds related to the metabolism of tyrosine. The mass spectra of all the studied compounds, recorded at several collision energies, are compared. The fragmentation mechanism of protonated molecules, MH⁺, is explained by combining collision‐induced dissociation (CID) mass spectra and density functional theory (DFT) calculations. The results show that the first fragmentation is the elimination from MH⁺ of a neutral molecule including a functional group of the linear chain. Three primary neutral losses are observed: 17 u (NH₃), 18 u (H₂O) and 46 u (H₂O+CO) characterizing amino, hydroxyl and carboxylic functions on the linear chain. The presence and abundance of ions corresponding to these losses are dependent on (i) the position of the functional group on the linear chain, (ii) the initial localisation of the protonating hydrogen, and (iii) the substitution of the aromatic ring. For compounds including a functional group on the benzylic carbon atom, the investigation of the other functions requires the knowledge of secondary fragmentations. Among these secondary fragmentations we have retained the loss of NH₃ from [MH–18u]⁺ and the loss of ketene from [MH–17u]⁺. Experimentally these fragmentations are detected using losses of 35 u and 59/73 u. In other words, NL35 identifies hydroxy and amino compounds and NL 46 and/or NL59/73 identify carboxylic acids. The search for characteristic neutral losses is used for the analysis of compounds in a mixture and the analysis of biological fluid. We show that selective search of several neutral losses allows also the unambiguous differentiation of isomers and gives the opportunity to identify compounds in biological fluids. Copyright © 2008 John Wiley & Sons, Ltd.     

Critères généraux de conception des réseaux de diodes lasers à rubans couplés par champs évanescents

The aim of this article is to define the general criteria for design of phase-locked diode laser arrays. A general method for designing these devices is presented using the effective index method and the coupled mode theory. The confinement required for the individual diodes is defined, and the allowed structure geometries are determined.     

Total synthesis of TMS-ent-bisabolangelone

The absolute configuration of bisabolangelone has been established by an eleven step total synthesis of the corresponding TMS protected antipode starting from (R)-(+)-pulegone. Comparison of the TMS-derivatives by GC on a chiral column, allowed us to assign the absolute configuration of the synthetic compound and thus of the corresponding natural product. The latter has been confirmed by the Mosher's ester analysis of the known secondary carbinol derivative.     

Electrochemical approach to detect the presence of peroxynitrite in aerobic neutral solution

This work describes the conditions of use of bare gold electrode to detect electrochemically the presence of peroxynitrite ONOO^? in phosphate buffer solution at pH 7.1. As ONOO^? is extremely unstable in neutral solution, current–potential curve was reconstructed between ?0.5 and 0.7 V vs SCE by amperometry experiments at rotating disk electrode at different potentials. Comparison of this reconstructed curve with voltammograms of the common interfering species (dopamine, hydrogen peroxide, nitrite, ascorbic acid and glutamate) shows that the presence of ONOO^? can be selectively determined at ?0.1 V vs SCE. This detection occurs through the electrochemical reduction of peroxynitrous acid ONOOH, the conjugated acid of ONOO^?. Detection of ONOO^? produced in situ by the reaction of nitric oxide with superoxide was also achieved.     

A stochastic evolution model for residue Insertion-Deletion Independent from Substitution

We develop here a new class of stochastic models of gene evolution based on residue Insertion-Deletion Independent from Substitution (IDIS). Indeed, in contrast to all existing evolution models, insertions and deletions are modeled here by a concept in population dynamics. Therefore, they are not only independent from each other, but also independent from the substitution process. After a separate stochastic analysis of the substitution and the insertion-deletion processes, we obtain a matrix differential equation combining these two processes defining the IDIS model. By deriving a general solution, we give an analytical expression of the residue occurrence probability at evolution time t as a function of a substitution rate matrix, an insertion rate vector, a deletion rate and an initial residue probability vector. Various mathematical properties of the IDIS model in relation with time t are derived: time scale, time step, time inversion and sequence length. Particular expressions of the nucleotide occurrence probability at time t are given for classical substitution rate matrices in various biological contexts: equal insertion rate, insertion-deletion only and substitution only. All these expressions can be directly used for biological evolutionary applications. The IDIS model shows a strongly different stochastic behavior from the classical substitution only model when compared on a gene dataset. Indeed, by considering three processes of residue insertion, deletion and substitution independently from each other, it allows a more realistic representation of gene evolution and opens new directions and applications in this research field.     

H(2) formation by electron irradiation of SBA-15 materials and the effect of Cu(II) grafting

Measurement of H(2) production from electron irradiation (10 MeV) on SBA-15 materials has shown that adsorbed water is attacked preferentially. Silanol groups are only attacked when they are in the majority with respect to adsorbed water, however they are much less efficient at producing H(2). The comparison between water content before and after electron irradiation and the corresponding H(2) production indicates that water desorption is the main route to adsorbed water loss for SBA-15 materials. On the other hand, surface silanol groups are more susceptible to attack, leading to H(2) production when SBA-15 samples have undergone extensive thermal treatment. Electron irradiation of SBA-15-Cu materials has shown that the presence of Cu(II) on the surface reduces and inhibits the production of H(2.) This inhibiting power affects adsorbed water bonded to grafted copper but not surface silanol groups.     

Expanded Pyridiniums: Bis‐cyclization of Branched Pyridiniums into Their Fused Polycyclic and Positively Charged Derivatives—Assessing the Impact of Pericondensation on Structural,Electrochemical, Electronic,and Photophysical Features

This study evaluates the impact of the extension of the π‐conjugated system of pyridiniums on their various properties. The molecular scaffold of aryl‐substituted expanded pyridiniums (referred to as branched species) can be photochemically bis‐cyclized into the corresponding fused polycyclic derivatives (referred to as pericondensed species). The representative 1,2,4,6‐tetraphenylpyridinium ( 1^H ) and 1,2,3,5,6‐pentaphenyl‐4‐(p‐tolyl)pyridinium ( 2^Me ) tetra‐ and hexa‐branched pyridiniums are herein compared with their corresponding pericondensed derivatives, the fully fused 9‐phenylbenzo[1,2]quinolizino[3,4,5,6‐def]phenanthridinium ( 1^H f ) and the hitherto unknown hemifused 9‐methyl‐1,2,3‐triphenylbenzo[h]phenanthro[9,10,1‐def]isoquinolinium ( 2^Me f ). Combined solid‐state X‐ray crystallography and solution NMR experiments showed that stacking interactions are barely efficient when the pericondensed pyridiniums are not appropriately substituted. The electrochemical study revealed that the first reduction process of all the expanded pyridiniums occurs at around ?1 V vs. SCE, which indicates that the lowest unoccupied molecular orbital (LUMO) remains essentially localized on the pyridinium core regardless of pericondensation. In contrast, the electronic and photophysical properties are significantly affected on going from branched to pericondensed pyridiniums. Typically, the number of absorption bands increases with extended activity towards the visible region (down to ca. 450 nm in MeCN), whereas emission quantum yields are increased by three orders of magnitude (at ca. 0.25 on average). A relationship is established between the observed differential impact of the pericondensation and the importance of the localized LUMO on the properties considered: predominant for the first reduction process compared with secondary for the optical and photophysical properties.