Photophysics,Electrochemistry and Efficient Electrochemiluminescence of Trigonal Truxene-Core Dyes

We synthesized and characterized a series of dyes built from a spirofluorene or truxene core. The quadrupolar spirofluorene system is the initial building unit for the design and preparation of more complex star-shaped dyes consisting of a truxene core bearing three di- or triphenylamine moieties with or without a thiophene connector. Their photophysical, electrochemical, and electrochemiluminescence (ECL) properties were first investigated in solution. Structure/activity relationships were derived and rationalized by comparing the quadrupolar system and trigonal truxene-core derivatives using computational studies. The photophysical and redox characteristics are drastically tuned by the introduction of a thiophene bridge and electron-donor substituents at their terminal branches. These comparative studies show the essential role of the stability of both radical cations and anions to obtain efficient ECL dyes. The stabilization of the radicals is directly related to the charge delocalization due to the π-conjugation by the thiophene bridge. The brightest ECL is achieved by annihilation and coreactant (benzoyl peroxide) pathways with the blue-emitting truxene dye, which is 2- and 4.5-times greater than that of the quadrupolar compound and reference [Ru(bpy)₃]²⁺ emitter, respectively. Such an extensive study on these extended π-conjugated molecules presenting different core structures may guide the design and synthesis of new ECL dyes with a strong efficiency.     

Experimentelle Beitr?ge zur quantitativen Spektralanalyse

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O-Demethylation of Opioid Derivatives with Methane Sulfonic Acid/ Methionine: Application to the Synthesis of Naloxone and Analogues

Naloxone 2 was obtained by demethylation of N-allylnoroxycodone 1 with methane sulfonic acid / methionine. This reagent is an excellent substitute for boron tribromide. It was used for the synthesis of analogous derivatives with variable results.     

Asymmetric palladium-catalyzed annulation of benzene-1,2-diol and racemic secondary propargylic carbonates bearing two different substituents

The palladium-catalyzed cyclization of benzene-1,2-diol with various racemic secondary propargyl carbonates having no acetylenic hydrogen in the presence of (R)-Binap as the chiral ligand afforded the two regioisomers of the corresponding 2,3-dihydro-1,4-dioxin derivatives in quite good yields, and also in enantioselectivities going from 40 to 97%. The cyclization of benzene-1,2-diol with methyl (R)-1-methyl-3-phenylpro-2-yn-1-yl carbonate in the presence of dppb as the achiral ligand afforded 2-benzylidene-3-methyl-2,3-dihydro-1,4-benzodioxine as the major product with 15% ee. The use of (R)-Binap as the chiral ligand afforded the (+) cyclized compound in 45% ee, when the (−) enantiomer was obtained with 77% ee in the presence of (S)-Binap. All the results suggest that in this case the enantioselective step is the diastereoselective protonation of the palladium-carbene intermediates.     

Numerical simulation of three-dimensional duct flows of incompressible fluids by using the stream-tube method

Numerical simulation of three-dimensional flows generally involves solving large-scale problems. In this paper we consider the stream-tube method in three-dimensional duct flows. The analysis uses the concept of stream tubes in a mapped computational domain of the physical domain where the streamlines are parallel and straight. The incompressibility equation is automatically verified and the primary unknowns of the problem are, in addition to the pressure, the transformation functions between the two domains. It is also shown that the flow may be computed by considering successive subdomains (the stream tubes). This results in a reduction of computing time and storage area. Incompressible viscous and elastic liquids involving memory-integral equations may be considered in the flow simulations. This part of the paper examines three-dimensional flows of Newtonian fluids. The method is applied to the flow in a duct involving a threefold rotational symmetry, where the discretized relevant equations are solved by using the Levenberg-Marquardt algorithm.     

Modelization of extensional experiments under constant force using memory-integral constitutive equations and stream-tube analysis

In this paper, we propose a numerical simulation of axisymmetric extensional experiments on a viscoelastic polydimethylsiloxane (PDMS) material, using a falling-weight extensional rheometer. The polymer behaviour is represented by a K-BKZ memory-integral constitutive equation, involving a damping function of the Wagner type. Under the assumption of a homogeneous flow zone in the sample, a numerical model is set up, using the stream-tube method and approximating functions. The governing equations of the problem, associated to a limited number of unknowns, are solved by means of the Levenberg-Marquardt optimization algorithm. The numerical results are found to be consistent with the experimental data and reveal the importance of the non-homogeneous flow zone, in relation to the estimation of the extensional strain rate. The calculations involve the sensitivity of the model on the fluid parameters and those concerning the size of the initial column of fluid. The limited computing (CPU) time of the code is also to be underlined.     

Modified Isoindolediones as Bright Fluorescent Probes for Cell and Tissue Imaging

New L -shaped fluorophores possessing five conjugated rings have been synthesized through a four-step procedure involving diketopyrrolopyrrole synthesis and its double N-alkylation, followed by trimethylsilyl bromide-mediated rearrangement to thieno[2,3-f]isoindole-5,8-dione and an intramolecular Friedel–Crafts reaction. In comparison with the parent isoindolediones and π-expanded diketopyrrolopyrroles, these new dyes show red-shifted absorption and emission (up to ≈630 nm). Their structural rigidity is responsible for both the observed small Stokes shifts and large fluorescence quantum yields. Tissue imaging studies revealed that these new dyes show advantageous features including minimal autofluorescence interference and pronounced solvent-sensitive emission. Interestingly, there is a fundamental difference between a dye possessing an amino group and its analog bearing an N-alkyl substituent. The former dye under two-photon excitation at 900 nm gives bright images whereas its N-alkylated counterpart does not. A new type of membrane localization has been discovered by an N-alkylated isoindoledione possessing a benzofuryl substituent. In spite of the fact that the fluorescence quantum yield of this dye in a range of solvents is rather low, it does stain cell membranes exclusively. This new mode of cellular staining opens the door towards further development of membrane staining dyes.