Synthetic Organic Design for Solar Fuel Systems

From the understanding of biological processes and metalloenzymes to the development of inorganic catalysts, electro‐ and photocatalytic systems for fuel generation have evolved considerably during the last decades. Recently, organic and hybrid organic systems have emerged to challenge the classical inorganic structures through their enormous chemical diversity and modularity that led earlier to their success in organic (opto)electronics. This Minireview describes recent advances in the design of synthetic organic architectures and promising strategies toward (solar) fuel synthesis, highlighting progress on materials from organic ligands and chromophores to conjugated polymers and covalent organic frameworks.     

Mechanism of formation of cyclic species in cationic ring-opening polymerization of cyclodimethylsiloxanes

A general feature of the cationic polymerization of all cyclodimethylsiloxanes is the formation of various cyclic products (cyclics) together with that of a linear high polymer. However, the types of cyclics as well as their rate of formation may vary considerably according to the number x of D units ((CH₃)₂SiO units) in the monomer. The case of initiation by trifluoromethanesulfonic (triflic) acid in methylene chloride solution at 20°C has been particularly studied. With D₄, D₅, D₆ and D₇, for which the polymerization rate increases with the size of the ring, all types of cycles D_x are formed in relative amount decreasing with their size ([D₇] < [D₆] < [D₅] < [D₄]). The high polymer final concentration and molecular weight are independent from triflic acid concentration. This may result from a polymerization-depolymerization reaction, involving all the cyclics formed by back-biting reactions occurring with silyl triflates activated by the acid, and leading finally to an equilibrium. The situation with D₃ is completely different. The high polymer (HP) and the cyclics (D_3x multiples of D₃ like D₆, D₉, …) are formed simultaneously under kinetic control. The yields of the various cyclics (formed in amount often larger than that of the HP) are proportional to that of the linear HP. The latter is formed from the beginning of the reaction with a molecular weight proportional to HP yield and inversely proportional to the acid concentration. The opposite role of added water on the polymerization is discussed: an activating effect for D₃, and a desactivating one for D₄, D₅ and D₆. “Copolymerization” experiments between D₃ (or D₄) and tetramethyldisiloxane diol confirmed the effect of water and gave new informations about the occurrence - or absence - of condensation reactions in the mechanism of the growth of the polymer chains. A discussion leads to the conclusion that while the cationic polymerization of D₄ by triflic acid is propagated by activated triflic esters, that of D₃ may also involve the monomer activated by the higher hydrates of the acid and linear oligomeric silanol esters. The latter, formed continuously, may also give the D_3x cyclics by intramolecular heterocondensation.     

Optimization of Hydrogen‐Evolving Photochemical Molecular Devices

A molecular photocatalyst consisting of a Ru^II photocenter, a tetrapyridophenazine bridging ligand, and a PtX₂ (X=Cl or I) moiety as the catalytic center functions as a stable system for light‐driven hydrogen production. The catalytic activity of this photochemical molecular device (PMD) is significantly enhanced by exchanging the terminal chlorides at the Pt center for iodide ligands. Ultrafast transient absorption spectroscopy shows that the intramolecular photophysics are not affected by this change. Additionally, the general catalytic behavior, that is, instant hydrogen formation, a constant turnover frequency, and stability are maintained. Unlike as observed for the Pd analogue, the presence of excess halide does not affect the hydrogen generation capacity of the PMD. The highly improved catalytic efficiency is explained by an increased electron density at the Pt catalytic center, this is confirmed by DFT studies.     

Gelatin‐Alginate Gels and Their Enzymatic Modifications: Controlling the Delivery of Small Molecules

The release of molecules entrapped within biogels is dictated by diffusion laws. Innovative biogel architectures are conceived and tested to control small molecule delivery from gelatin gels. The ionic interactions modulate the release of small molecules. Alginate is then added to gelatin gels and further hydrolyzed; the influence of viscosity is discussed. Next, various mixed gels are compared, such as a gelatin‐alginate IPN and the original architecture of an alginate gel entrapped in a gelatin gel with or without a polysaccharidase. The relative influence of ionic interactions and diffusional constraints on the delivery of small charged molecules is explored, and a solution for controlling diffusion is proposed for any situation.

     

Heat-treatment studies of molybdenum oxide-monohydrate

The dehydration of molybdic acid, MoO₃---H₂O, was studied by thermal analysis, X-ray diffractometry and FTIR spectroscopy. The results show that an intermediate phase, MoO₃-2/3H₂O is formed at 216 °C and the monoclinic form of MoO₃ is grown above 350 °C. The mechanism of dehydration and structural rearrangement were confirmed by the features of the infrared spectra showing formation of corner-shared MoO₆ octahedra.     

On the Second Cohomology of K?hler Groups

Carlson and Toledo conjectured that if an infinite group Γ is the fundamental group of a compact K?hler manifold, then virtually H²(G, \mathbb R) 1 0{H^{2}(\Gamma, {\mathbb R}) \ne 0} . We assume that Γ admits an unbounded reductive rigid linear representation. This representation necessarily comes from a complex variation of Hodge structure ( \mathbbC{\mathbb{C}} -VHS) on the K?hler manifold. We prove the conjecture under some assumption on the \mathbbC{\mathbb{C}} -VHS. We also study some related geometric/topological properties of period domains associated to such a \mathbbC{\mathbb{C}} -VHS.     

High-field magnetic phases of a two-leg spin ladder: Cu2(C5H12N2)2Cl4

CHCupCl is a two-leg spin-ladder where the Cu⁺⁺ ions are coupled by superexchange. Its magnetic properties change dramatically as a function of a magnetic field. Below the critical field H_c1, there is a singlet ground state separated from the triplet excited state by an energy gap. Between H_c1 and H_c2, several magnetic phases have been observed. Above 1 K, dynamical studies reveal a disordered quantum critical phase. At lower temperatures, a 3-D ordered phase has been observed in specific heat and NMR studies. New NMR results on the 3D-ordered and quantum critical phases are presented in this short report.     

Characterization Theorem for Best Polynomial Spline Approximation with Free Knots,Variable Degree and Fixed Tails

In this paper, we derive a necessary condition for a best approximation by piecewise polynomial functions of varying degree from one interval to another. Based on these results, we obtain a characterization theorem for the polynomial splines with fixed tails, that is the value of the spline is fixed in one or more knots (external or internal). We apply nonsmooth nonconvex analysis to obtain this result, which is also a necessary and sufficient condition for inf-stationarity in the sense of Demyanov–Rubinov. This paper is an extension of a paper where similar conditions were obtained for free tails splines. The main results of this paper are essential for the development of a Remez-type algorithm for free knot spline approximation.     

Nonsmooth nonconvex optimization approach to clusterwise linear regression problems

Clusterwise regression consists of finding a number of regression functions each approximating a subset of the data. In this paper, a new approach for solving the clusterwise linear regression problems is proposed based on a nonsmooth nonconvex formulation. We present an algorithm for minimizing this nonsmooth nonconvex function. This algorithm incrementally divides the whole data set into groups which can be easily approximated by one linear regression function. A special procedure is introduced to generate a good starting point for solving global optimization problems at each iteration of the incremental algorithm. Such an approach allows one to find global or near global solution to the problem when the data sets are sufficiently dense. The algorithm is compared with the multistart Späth algorithm on several publicly available data sets for regression analysis.