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.     

Perfect extinction in subwavelength dual metallic transmitting gratings

We investigate the strong electromagnetic coupling that settles in dual metallic grating structures. This coupling is evidenced to lead to a perfect optical extinction in the transmission spectrum. The behavior of this perfect extinction that strongly depends on the longitudinal space and the lateral displacement between the two gratings can be explained by a simple model that describes the interference between a propagating mode and a couple of evanescent modes. The results show that the electromagnetic transmission of the structure can be tuned by controlling the position of this perfect transmission extinction and thus pave the way to new types of infrared tunable filters.     

Subpicosecond pulse generation from a 1.56 μm mode-locked VECSEL

Near-transform-limited subpicosecond pulses at 1.56 μm were generated from an optically pumped InP-based vertical-external-cavity surface-emitting laser (VECSEL) passively mode-locked at 2 GHz repetition rate with a fast InGaAsNSb/GaAs semiconductor saturable absorber mirror (SESAM). The SESAM microcavity resonance was adjusted via a selective etching of phase layers specifically designed to control the magnitude of both the modulation depth and the intracavity group delay dispersion of the SESAM. Using the same VECSEL chip, we observed that the mode-locked pulse duration could be reduced from several picoseconds to less than 1 ps with a detuned resonant SESAM.     

Modulation of amyloid-β aggregation by metal complexes with a dual binding mode and their delivery across the blood–brain barrier using focused ultrasound

One of the key hallmarks of Alzheimer''s disease is the aggregation of the amyloid-β peptide to form fibrils. Consequently, there has been great interest in studying molecules that can disrupt amyloid-β aggregation. While a handful of molecules have been shown to inhibit amyloid-β aggregation in vitro, there remains a lack of in vivo data reported due to their inability to cross the blood–brain barrier. Here, we investigate a series of new metal complexes for their ability to inhibit amyloid-β aggregation in vitro. We demonstrate that octahedral cobalt complexes with polyaromatic ligands have high inhibitory activity thanks to their dual binding mode involving π–π stacking and metal coordination to amyloid-β (confirmed via a range of spectroscopic and biophysical techniques). In addition to their high activity, these complexes are not cytotoxic to human neuroblastoma cells. Finally, we report for the first time that these metal complexes can be safely delivered across the blood–brain barrier to specific locations in the brains of mice using focused ultrasound.

We report a series of non-toxic cobalt(iii) complexes which inhibit Aβ peptide aggregation in vitro; these complexes can be safely delivered across the blood–brain barrier in mice using focused ultrasound.     

Poly­[lead(II)‐μ2‐aqua‐μ4‐tereph­thalato]

The title compound, [Pb(C₈H₄O₄)(H₂O)]_n, forms as an insoluble product in the reaction of sodium terephthalate(2−) with Pb(NO₃)₂ in water. Analysis has shown that the crystal structure is centrosymmetric, with the asymmetric unit containing one formula unit. The lead geometry is hemidirected seven‐coordinate, with both monodentate and bidentate carboxyl­ate coordination modes present. The combination of hydrogen bonds and coordination bonds produces a three‐dimensional structure, including the first example, in a lead complex, of the common metal‐coordinated carboxyl­ate/water (6) graph‐set motif.