Recent developments in the synthesis and functionalization of conducting poly(thiophenes)

The mechanism of the electropolymerization of thiophene derivatives has been investigated by varying the electrosynthesis conditions and the monomer structure. The results of these analyses led to the definition of optimized electrosynthesis conditions allowing the control of the electrical and electrochemical properties of poly(thiophenes). On the basis of these results, the properties of these polymers have been modified by means of a new one-step electrosynthesis of conducting composite materials and by the direct electropolymerization of tailor-made functionalized monomers. For this purpose, the steric conditions associated to the various possibilities of covalent derivatization have been analyzed, leading to the definition of a “functionalization space”, compatible with the preservation of high conductivity and electrochemical reversibility in the resulting polymers. This concept has been applied to the synthesis of highly conducting chiral poly(thiophenes) on which an effect of enantioselective molecular recognition has been demonstrated for the first time.     

Chemical modification of poly(lactic acid) induced by thermal decomposition of N‐acetoxy‐phthalimide during extrusion

Chemical modification of poly(lactic acid) (PLA) with N‐acetoxy‐phthalimide (NAPI) was performed in the melt by reactive extrusion, without using any peroxide initiator. The aminyl and nitroxide radicals produced from the NAPI thermal degradation, were, respectively, used (a) to create PLA macroradicals, and (b) to functionalize the PLA samples through nitroxide radical coupling. Depending on the extrusion temperature and the initial NAPI concentration, grafting rates up to 0.24 mol % were measured, modifying the PLA optical properties. This study represents an original new way of modification of PLA without the use of conventional peroxide initiators. Indeed, the undesirable side reactions (PLA branching or crosslinking) usually observed when using peroxides to initiate the radical grafting of PLA were avoided when using NAPI. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 120–129     

Pierre Turq,an inspirational scientist in charge and at interfaces

Pierre Turq has made decisive contributions to the theory and to the multiscale simulation of charged systems, such as molten salts, electrolyte solutions and colloidal suspensions, in the bulk, at interfaces and under confinement. His research line focussed on dynamical properties and was characterised by constant efforts to connect his theoretical work to both experiments and practical applications. In this article, his colleagues and former students pay a tribute to his past and current research interests by illustrating some recent developments accomplished in his laboratory.     

On well-posedness for some dispersive perturbations of Burgers' equation

We show that the Cauchy problem for a class of dispersive perturbations of Burgers' equations containing the low dispersion Benjamin–Ono equation

${?}_{t}u?D_x^{\alpha }{?}_{x}u={?}_x(u^2),0<\alpha \le 1,$

is locally well-posed in $H^s(\mathbb{R})$ when $s>s_{\alpha }:=\frac{3}{2}?\frac{5\alpha }{4}$. As a consequence, we obtain global well-posedness in the energy space $H^{\frac{\alpha }{2}}(\mathbb{R})$ as soon as $\frac{\alpha }{2}>s_{\alpha }$, i.e. $\alpha >\frac{6}{7}$.     

Practical use of variational principles for modeling water waves

This paper describes a method for deriving approximate equations for irrotational water waves. The method is based on a ‘relaxed’ variational principle, i.e., on a Lagrangian involving as many variables as possible. This formulation is particularly suitable for the construction of approximate water wave models, since it allows more freedom while preserving a variational structure. The advantages of this relaxed formulation are illustrated with various examples in shallow and deep waters, as well as arbitrary depths. Using subordinate constraints (e.g., irrotationality or free surface impermeability) in various combinations, several model equations are derived, some being well-known, other being new. The models obtained are studied analytically and exact traveling wave solutions are constructed when possible.     

Comprehensive two-dimensional gas chromatography for enhanced analysis of naphthas: new column combination involving permethylated cyclodextrin in the second dimension

A new column association using comprehensive two-dimensional gas chromatography for the detailed molecular analysis of hydrocarbon mixtures is reported in this paper. In order to compare the impact of two different secondary columns, a novel column combination relying on a GC x 2GC system was used. This system is based on a non-polar first column (PONA) combined with both a permethylated beta-cyclodextrin (beta-Dex 120) stationary phase and a polysilphenylensiloxane (BPX 50) in the second dimension. Compared to BPX 50 stationary phase, the implementation of beta-cyclodextrin columns as the second dimension was found to improve the resolution between paraffins and naphthenes in the naphtha range but not in the middle distillate range. Attempts to improve the results and to understand the interaction mechanism remained unsuccessful. Therefore, the benefits of the beta-Dex 120-column are only demonstrated on heavy naphtha cut for the quantitation of hydrocarbons.     

Walking metals in d8···d8 hetero-bimetallic complexes: an original dynamic phenomenon

In the course of our investigations on polymetallic complexes derived from 1,3-bis(thiophosphinoyl)indene (Ind(Ph(2)P=S)(2)), we observed original fluxional behavior and report herein a joint experimental/computational study of this dynamic process. Starting from the indenylidene chloropalladate species [Pd{Ind(Ph(2) P=S)(2)}Cl](-) (1), the new Pd(II)···Rh(I) hetero-bimetallic pincer complex [PdCl{Ind(Ph(2) P=S)(2)}Rh(nbd)] (2; nbd=2,5-norbornadiene) was prepared. X-ray crystallography and DFT calculations substantiate the presence of a d(8)···d(8) interaction. According to multinuclear variable-temperature NMR spectroscopic experiments, the pendant {Rh(nbd)} fragment of 2 readily shifts in solution at room temperature between the two edges of the SCS tridentate ligand. To assess the role of the pincer-based polymetallic structure on this fluxional behavior, the related monometallic Rh complex [Rh{IndH(Ph(2) P=S)(2)}(nbd)] (3) was prepared. No evidence for a metal shift was observed in that case, even at high temperature, thus indicating that inplane pincer coordination to the Pd center plays a crucial role. The previously described Pd(II)···Ir(I) bimetallic complex 4 exhibited fluxional behavior in solution, but with a significantly higher activation barrier than 2. This finding demonstrates the generality of this metal-shift process and the strong influence of the involved metal centers on the associated activation barrier. DFT calculations were performed to shed light onto the mechanism of such metal-shift processes and to identify the factors that influence the associated activation barriers. Significantly different pathways were found for bimetallic complexes 2 and 4 on one hand and the monometallic complex 3 on the other hand. The corresponding activation barriers predicted computationally are in very good agreement with the experimental observations.     

Unsaturated four-membered N-heterocycles: From synthesis to applications

The ubiquity of strained motifs in drug discovery has recently witnessed a large regain of interest, as such scaffold can be used to modulate the properties of drug candidates. Unsaturated N-containing four-membered heterocycles present unique opportunities to access functionalized azetidines, which play an essential role in pharmacological studies. Even though those unsaturated patterns have been much less reported than the corresponding saturated versions, the consequent impact that those structures could have on molecular design with implementation of strained modules deserves to be summarized. In this review, synthetic accesses to substituted azetes, 1-azetines and 2-azetines are depicted, as well as their involvement in further transformations.     

Synthesis of Renewable meta‐Xylylenediamine from Biomass‐Derived Furfural

We report the synthesis of biomass‐derived functionalized aromatic chemicals from furfural, a building block nowadays available in large scale from low‐cost biomass. The scientific strategy relies on a Diels–Alder/aromatization sequence. By controlling the rate of each step, it was possible to produce exclusively the meta aromatic isomer. In particular, through this route, we describe the synthesis of renewably sourced meta‐xylylenediamine (MXD). Transposition of this work to other furfural‐derived chemicals is also discussed and reveals that functionalized biomass‐derived aromatics (benzaldehyde, benzylamine, etc.) can be potentially produced, according to this route.