Copper Complexes as Alternative Redox Mediators in Dye-Sensitized Solar Cells

Thirty years ago, dye-sensitized solar cells (DSSCs) emerged as a method for harnessing the sun’s energy and converting it into electricity. Since then, a lot of work has been dedicated to improving their global photovoltaic efficiency and their eco-sustainability. Recently, various articles showed the great potential of copper complexes as a convenient and cheap alternative to the traditional ruthenium dyes. In addition, copper complexes demonstrate that they can act as redox mediators for DSSCs, thus being an answer to the problems related to the I₃⁻/I⁻ redox couple. The aim of this review is to report on the most recent impact made by copper complexes as alternative redox mediators. The coverage, mainly from 2016 up to now, is not exhaustive, but allows us to understand the great role played by copper complexes in the design of eco-sustainable DSSCs.     

On Bayes estimators with uniform priors on spheres and their comparative performance with maximum likelihood estimators for estimating bounded multivariate normal means

For independently distributed observables: X_i∼N(θ_i,σ²),i=1,…,p, we consider estimating the vector θ=(θ₁,…,θ_p)^′ with loss ‖d−θ‖² under the constraint , with known τ₁,…,τ_p,σ²,m. In comparing the risk performance of Bayesian estimators δ_α associated with uniform priors on spheres of radius α centered at (τ₁,…,τ_p) with that of the maximum likelihood estimator , we make use of Stein’s unbiased estimate of risk technique, Karlin’s sign change arguments, and a conditional risk analysis to obtain for a fixed (m,p) necessary and sufficient conditions on α for δ_α to dominate . Large sample determinations of these conditions are provided. Both cases where all such δ_α’s and cases where no such δ_α’s dominate are elicited. We establish, as a particular case, that the boundary uniform Bayes estimator δ_m dominates if and only if m≤k(p) with , improving on the previously known sufficient condition of Marchand and Perron (2001) [3] for which . Finally, we improve upon a universal dominance condition due to Marchand and Perron, by establishing that all Bayesian estimators δ_π with π spherically symmetric and supported on the parameter space dominate whenever m≤c₁(p) with .     

Physically and Chemically Crosslinked Gelatin Gels

In this paper, we examine the rheological and the structural properties of different types of gelatin networks, physical, chemical and both. The physical gel is due to the formation of collagen type triple helices when cooling the solutions. Chemically crosslinked gels are obtained with a reagent, in our case the bis(vinylsulfonyl)methane (BVSM), kindly provided by Kodak Industrie (France). Each BVSM molecule provides two covalent bonds. The chemical reaction was followed by microcalorimetry (MicroDSC III from Setaram, Caluire, France). The relation between shear moduli and crosslinking for the three types of gels is discussed, in relation with theoretical models of randomly crosslinked systems.     

New insights in the search for chiral Brønsted bases

The concept of using chiral bases in asymmetric synthesis appeared with the emergence of the chemistry of chiral lithium amides. In recent years, new classes of chiral bases, such as chiral magnesium bisamides and chiral alkali alkoxides have proven to be highly efficient and easy to handle. This paper highlights recent advances and new concepts in the chemistry of this second generation of chiral bases.     

Thiolate chemistry: a powerful and versatile synthetic tool for immobilization/functionalization of oligothiophenes on a gold surface

The synthesis and characterization of a series of quaterthiophenes (4Ts) with thiolate groups protected with 2-cyanoethyl (CNE), 2-trimethylsilylethyl (TMSE), and acetyl (Ac) groups are described. Sequential cleavage of these different protecting groups allows for the preparation of 4Ts derivatized with ferrocene and/or alkanethiol chains. The electrochemical behavior of these compounds has been analyzed in solution by cyclic voltammetry (CV). A ferrocene-derivatized dithiol 4T 14 and a dithiol 4T 15 with two TMSE-protected thiolate groups have been immobilized on a gold surface as monolayers that have been characterized by CV, ellipsometry, contact-angle measurement, and X-ray photoelectron spectroscopy (XPS). The results show that molecules 14 and 15 are doubly grafted with a horizontal orientation of the conjugated system relative to the surface. Furthermore, application of the deprotection/alkylation sequence of the remaining protected thiolate groups on a monolayer of 15 allows for efficient post-functionalization.     

Syntheses of l-glucosamine donors for 1,2-trans-glycosylation reactions

Two new l-glucosamine donors, that is pent-4-enyl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-β-l-glucopyranoside 16 and ethyl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-1-thio-β-l-glucopyranoside 21 were prepared in 12 steps from l-arabinose. The reaction pathway uses 3,4,6-tri-O-acetyl-l-glucal 5, and then 3,4,6-tri-O-acetyl-2-deoxy-2-iodo-α-l-mannopyranosyl azide 8 as intermediates. The latter, together with donors 16 and 21, were used for preparing l-glucosamine neoglycolipids.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Effects of Some Hydrotropic Agents on the Formation of Indomethacin/β-Cyclodextrin Inclusion Compounds

The influence of the water structure promoters, mannitol and sucrose, on the indomethacin/-cyclodextrin inclusion process at different pH values was evaluated using the phase solubility method and circular dichroism spectroscopy. The effect of mannitol and sucrose on the total solubilizing activity of -cyclodextrin as well as on the stabilization of the complex was moderate, and depended strongly on the pH value of the medium. The most pronounced effect on the association constant of the indomethacin inclusion compound was observed in KCl/HCl buffer of pH 1.6, because mannitol and sucrose, in the absence of -cyclodextrin, approximately double the indomethacin solubility so that the constant value decreases. On the other hand, a very strong complex formation between indomethacin and -cyclodextrin was observed in acid medium (KCl/HCl buffer, pH = 1.6), a fact not much discussed in the literature. The apparent association constant of the inclusion compound formed in the absence of mannitol or sucrose was found to be of the same order of magnitude as for the complex formed at pH 6.8. Changes in the optical activity of the indomethacin/-cyclodextrin inclusion complex were registered in the presence of sucrose, which interacts more strongly than mannitol with water molecules, and could probably adhere to the surface of the inclusion complex, thus changing its configuration and environment.