Reaction of anthracene with CH radicals: an experimental study of the kinetics between 58 and 470 K

The rate coefficient of the reaction of the methylidine radical CH with anthracene has been studied over a wide temperature range (58-470 K) in a dedicated "Cinétique de Réaction en Ecoulement Supersonique Uniforme" (Reaction Kinetics in Uniform Supersonic Flow) apparatus. The reaction exhibits a slight positive temperature dependence, which can be fitted to the expression k(T) = (3.32 +/- 1.00) x 10(-10)(T/298)((0.46+/-0.14)) cm3 molecule(-1) s(-1). Even at the lowest temperature, the reaction remains very fast indicating that the kinetics are probably driven by a capture process.     

Photophysics of a series of efficient fluorescent pH probes for dual-emission-wavelength measurements in aqueous solutions

This paper evaluates the 5-aryl-2-pyridyloxazole backbone to engineer donor-acceptor fluorescent pH probes after one- or two-photon absorption. Parent fluorophores, as well as derivatives that can be used to label biomolecules, can be easily obtained in good yields. These molecules exhibit a large one-photon absorption in the near-UV range, and a strong fluorescence emission that covers the whole visible domain. The 5-aryl-2-pyridyloxazole derivatives also possess significant cross sections for two-photon absorption. Upon pyridine protonation, large shifts were observed in the absorption spectra after one- and two-photon excitation, as well as in the emission spectra. This feature was used to measure the pK(a) of the investigated compounds that range between 2 and 8. In most of the investigated derivatives, the pK(a) increased upon light excitation and protonation exchanges took place during the lifetime of the excited state, as shown by phase-modulation fluorometry analysis. Several 5-aryl-2-pyridyloxazole derivatives are suggested as efficient probes to reliably measure the pH of aqueous solutions by means of ratiometric methods that are dependent on fluorescence emission.     

One-pot synthesis of 5-arylidene-2-imino-4-thiazolidinones under microwave irradiation

A rapid and easy solvent free one-pot synthesis of 5-arylidene-2-imino-4-thiazolidinones by condensation of the thioureas with chloroacetic acid and an aldehyde under microwave-irradiation is described.     

Continuity of optimal transport maps and convexity of injectivity domains on small deformations of 𝕊2

Given a compact Riemannian manifold, we study the regularity of the optimal transport map between two probability measures with cost given by the squared Riemannian distance. Our strategy is to define a new form of the so‐called Ma‐Trudinger‐Wang condition and to show that this condition, together with the strict convexity on the nonfocal domains, implies the continuity of the optimal transport map. Moreover, our new condition, again combined with the strict convexity of the nonfocal domains, allows us to prove that all injectivity domains are strictly convex too. These results apply, for instance, on any small C⁴‐deformation of the 2‐sphere. © 2009 Wiley Periodicals, Inc.     

Slippage and nanorheology of thin liquid polymer films

Thin liquid films on surfaces are part of our everyday life; they serve, e.g.,?as coatings or lubricants. The stability of a thin layer is governed by interfacial forces, described by the effective interface potential, and has been subject of many studies in recent decades. In recent years, the dynamics of thin liquid films has come into focus since results on the reduction of the glass transition temperature raised new questions on the behavior of especially polymeric liquids in confined geometries. The new focus was fired by theoretical models that proposed significant implication of the boundary condition at the solid/liquid interface on the dynamics of dewetting and the form of a liquid front. Our study reflects these recent developments and adds new experimental data to corroborate the theoretical models. To probe the solid/liquid boundary condition experimentally, different methods are possible, each bearing advantages and disadvantages, which will be discussed. Studying liquid flow on a variety of different substrates entails a view on the direct implications of the substrate. The experimental focus of this study is the variation of the polymer chain length; the results demonstrate that inter-chain entanglements and in particular their density close to the interface, originating from non-bulk conformations, govern the liquid slip of a polymer.     

Reactive force field potential for carbon deposition on silicon surfaces

In this paper a new interatomic potential based on the Kieffer force field and designed to perform molecular dynamics (MD) simulations of carbon deposition on silicon surfaces is implemented. This potential is a third-order reactive force field that includes a dynamic charge transfer and allows for the formation and breaking of bonds. The parameters for Si-C and C-C interactions are optimized using a genetic algorithm. The quality of the potential is tested on its ability to model silicon carbide and diamond physical properties as well as the formation energies of point defects. Furthermore, MD simulations of carbon deposition on reconstructed (100) silicon surfaces are carried out and compared to similar simulations using a Tersoff-like bond order potential. Simulations with both potentials produce similar results showing the ability to extend the use of the Kieffer potential to deposition studies. The investigation reveals the presence of a channelling effect when depositing the carbon at 45°?incidence angle. This effect is due to channels running in directions symmetrically equivalent to the (110) direction. The channelling is observed to a lesser extent for carbon atoms with 30°?and 60°?incidence angles relative to the surface normal. On a pristine silicon surface, sticking coefficients were found to vary between 100 and 73%, depending on deposition conditions.     

A note on utility based pricing and asymptotic risk diversification

In principle, liabilities combining both insurancial risks (e.g. mortality/longevity, crop yield,...) and pure financial risks cannot be priced neither by applying the usual actuarial principles of diversification, nor by arbitrage-free replication arguments. Still, it has been often proposed in the literature to combine these two approaches by suggesting to hedge a pure financial payoff computed by taking the mean under the historical/objective probability measure on the part of the risk that can be diversified. Not surprisingly, simple examples show that this approach is typically inconsistent for risk adverse agents. We show that it can nevertheless be recovered asymptotically if we consider a sequence of agents whose absolute risk aversions go to zero and if the number of sold claims goes to infinity simultaneously. This follows from a general convergence result on utility indifference prices which is valid for both complete and incomplete financial markets. In particular, if the underlying financial market is complete, the limit price corresponds to the hedging cost of the mean payoff. If the financial market is incomplete but the agents behave asymptotically as exponential utility maximizers with vanishing risk aversion, we show that the utility indifference price converges to the expectation of the discounted payoff under the minimal entropy martingale measure.     

Photosubstitution in a trisheteroleptic ruthenium complex inhibits conjunctival melanoma growth in a zebrafish orthotopic xenograft model

In vivo data are rare but essential for establishing the clinical potential of ruthenium-based photoactivated chemotherapy (PACT) compounds, a new family of phototherapeutic drugs that are activated via ligand photosubstitution. Here a novel trisheteroleptic ruthenium complex [Ru(dpp)(bpy)(mtmp)](PF₆)₂ ([2](PF₆)₂, dpp = 4,7-diphenyl-1,10-phenanthroline, bpy = 2,2′-bipyridine, mtmp = 2-methylthiomethylpyridine) was synthesized and its light-activated anticancer properties were validated in cancer cell monolayers, 3D tumor spheroids, and in embryonic zebrafish cancer models. Upon green light irradiation, the non-toxic mtmp ligand is selectively cleaved off, thereby releasing a phototoxic ruthenium-based photoproduct capable notably of binding to nuclear DNA and triggering DNA damage and apoptosis within 24–48 h. In vitro, fifteen minutes of green light irradiation (21 mW cm⁻², 19 J cm⁻², 520 nm) were sufficient to generate high phototherapeutic indexes (PI) for this compound in a range of cancer cell lines including lung (A549), prostate (PC3Pro4), conjunctival melanoma (CRMM1, CRMM2, CM2005.1) and uveal melanoma (OMM1, OMM2.5, Mel270) cancer cell lines. The therapeutic potential of [2](PF₆)₂ was further evaluated in zebrafish embryo ectopic (PC3Pro4) or orthotopic (CRMM1, CRMM2) tumour models. The ectopic model consisted of red fluorescent PC3Pro4-mCherry cells injected intravenously (IV) into zebrafish, that formed perivascular metastatic lesions at the posterior ventral end of caudal hematopoietic tissue (CHT). By contrast, in the orthotopic model, CRMM1- and CRMM2-mCherry cells were injected behind the eye where they developed primary lesions. The maximally-tolerated dose (MTD) of [2](PF₆)₂ was first determined for three different modes of compound administration: (i) incubating the fish in prodrug-containing water (WA); (ii) injecting the prodrug intravenously (IV) into the fish; or (iii) injecting the prodrug retro-orbitally (RO) into the fish. To test the anticancer efficiency of [2](PF₆)₂, the embryos were treated 24 h after engraftment at the MTD. Optimally, four consecutive PACT treatments were performed on engrafted embryos using 60 min drug-to-light intervals and 90 min green light irradiation (21 mW cm⁻², 114 J cm⁻², 520 nm). Most importantly, this PACT protocol was not toxic to the zebrafish. In the ectopic prostate tumour models, where [2](PF₆)₂ showed the highest photoindex in vitro (PI > 31), the PACT treatment did not significantly diminish the growth of primary lesions, while in both conjunctival melanoma orthotopic tumour models, where [2](PF₆)₂ showed more modest photoindexes (PI ∼ 9), retro-orbitally administered PACT treatment significantly inhibited growth of the engrafted tumors. Overall, this study represents the first demonstration in zebrafish cancer models of the clinical potential of ruthenium-based PACT, here against conjunctival melanoma.

A new tris-heteroleptic photoactivated chemotherapy ruthenium complex induces apoptosis upon green light activation in a zebrafish orthothopic conjunctival melanoma xenograft model.     

Post-Modification of Copolymers Obtained by ATRP for an Application in Heterogeneous Asymmetric Salen Catalysis

Copolymers are valuable supports for obtaining heterogeneous catalysts that allow their recycling and therefore substantial savings, particularly in the field of asymmetric catalysis. This contribution reports the use of two comonomers: Azido-3-propylmethacrylate (AZMA) bearing a reactive azide function was associated with 2-methoxyethyl methacrylate (MEMA), used as a spacer, for the ATRP synthesis of copolymers, and then post-functionalized with a propargyl chromium salen complex. The controlled homopolymerization of MEMA by ATRP was firstly described and proved to be more controlled in molar mass than that of AZMA for conversions up to 63%. The ATRP copolymerization of both monomers made it possible to control the molar masses and the composition, with nevertheless a slight increase in the dispersity (from 1.05 to 1.3) when the incorporation ratio of AZMA increased from 10 to 50 mol%. These copolymers were post-functionalized with chromium salen units by click chemistry and their activity was evaluated in the asymmetric ring opening of cyclohexene oxide with trimethylsilyl azide. At an equal catalytic ratio, a significant increase in enantioselectivity was obtained by using the copolymer containing the largest part of salen units, probably allowing, in this case, the more favorable bimetallic activation of both the engaged nucleophile and electrophile. Moreover, the catalytic polymer was recovered by simple filtration and re-engaged in subsequent catalytic runs, up to seven times, without loss of activity or selectivity.     

Circularly Polarized Luminescence from Cyclic (Alkyl)(Amino) Carbene Derived Propellers

Organic circularly polarized luminescence (CPL)-active molecular emitters featuring dynamic propeller-like luminophores were prepared in one step from cyclic(alkyl)(amino) carbenes (CAACs). These molecules exhibit through-space arene-arene π-delocalization and rapid intramolecular inter-system crossing (ISC) in line with their helical character.