Biomimetic Total Synthesis of Santalin Y

A biomimetic total synthesis of santalin Y, a structurally complex but racemic natural product, is described. The key step is proposed to be a (3+2) cycloaddition of a benzylstyrene to a “vinylogous oxidopyrylium”, which is followed by an intramolecular Friedel–Crafts reaction. This cascade generates the unique oxafenestrane framework of the target molecule and sets its five stereocenters in one operation. Our work provides rapid access to santalin Y and clarifies its biosynthetic relationship with other colorants isolated from red sandalwood.     

Effect of spacer insertion in a commonly used dithienosilole/benzothiadiazole-based low band gap copolymer for polymer solar cells

Dithienosilole-benzothiadiazole based low bandgap copolymers remain promising material for organic photovoltaics. A new copolymer, poly[(4,4′-dioctyldithieno[3,2-b:2′,3′-d]silole-2,6-diyl)-alt-{4,7-bis[2-(3-hexyl)thienyl]-2,1,3-benzothiadiazole-5,5′-diyl}] (PDTSDTBT) was designed by introducing a thiophene spacer bearing a hexyl chain at β-position in the main backbone and compared to its analog poly[(4,4′-dioctyldithieno[3,2-b:2′,3′-d]silole-2,6-diyl)-alt-(2,1,3-benzothiadiazole-4,7-diyl)] (PDTSBT). In PDTSDTBT, linear alkyl chains on silicon were chosen due to facile and cheap access and the inserted 3-hexylthiophene units were chosen to increase solubility and molar mass, a weak point with PDTSBT. The two parameters are important to optimize photovoltaic performances. To compare characteristics, PDTSDTBT of molar masses greater than, and equal to a sample of PDTSBT, were prepared. Pd-catalyzed Stille cross-coupling reactions in a micro-wave reactor to promote an efficient copolymerisations. A strong absorption ranging from 370 nm to 800 nm and a good thermal stability were observed. PDTSDTBT showed better solubility and higher degree of crystallinity. Facile synthesis of high molar masses meant that higher efficiencies, around 40% greater, could be obtained with PDTSDTBT. The polymer was demonstrated to be susceptible to improvement through the use of device-additives. For example, under initial optimisations using PDTSDTBT:PC₆₀BM blend at a ratio of 1:1 delivered a power conversion efficiency of 2.13% with J_SC = 7.73 (mA/cm²), under AM 1.5 (100 mW/cm²) illumination.     

Analysis and synthesis of the three-dimensional movements of the head, face, and hand of a speaker using cued speech

In this paper we present efforts for characterizing the three dimensional (3-D) movements of the right hand and the face of a French female speaker during the audiovisual production of cued speech. The 3-D trajectories of 50 hand and 63 facial flesh points during the production of 238 utterances were analyzed. These utterances were carefully designed to cover all possible diphones of the French language. Linear and nonlinear statistical models of the articulations and the postures of the hand and the face have been developed using separate and joint corpora. Automatic recognition of hand and face postures at targets was performed to verify a posteriori that key hand movements and postures imposed by cued speech had been well realized by the subject. Recognition results were further exploited in order to study the phonetic structure of cued speech, notably the phasing relations between hand gestures and sound production. The hand and face gestural scores are studied in reference with the acoustic segmentation. A first implementation of a concatenative audiovisual text-to-cued speech synthesis system is finally described that employs this unique and extensive data on cued speech in action.     

A class of semidefinite programs with rank-one solutions

We show that a class of semidefinite programs (SDP) admits a solution that is a positive semidefinite matrix of rank at most r, where r is the rank of the matrix involved in the objective function of the SDP. The optimization problems of this class are semidefinite packing problems, which are the SDP analogs to vector packing problems. Of particular interest is the case in which our result guarantees the existence of a solution of rank one: we show that the computation of this solution actually reduces to a Second Order Cone Program (SOCP). We point out an application in statistics, in the optimal design of experiments.     

Twisted vortex filaments in the three-dimensional complex Ginzburg-Landau equation

The structure and dynamics of vortex filaments that form the cores of scroll waves in three-dimensional oscillatory media described by the complex Ginzburg-Landau equation are investigated. The study focuses on the role that twist plays in determining the bifurcation structure in various regions of the (alpha,beta) parameter space of this equation. As the degree of twist increases, initially straight filaments first undergo a Hopf bifurcation to helical filaments; further increase in the twist leads to a secondary Hopf bifurcation that results in supercoiled helices. In addition, localized states composed of superhelical segments interspersed with helical segments are found. If the twist is zero, zigzag filaments are found in certain regions of the parameter space. In very large systems disordered states comprising zigzag and helical segments with positive and negative senses exist. The behavior of vortex filaments in different regions of the parameter space is explored in some detail. In particular, an instability for nonzero twist near the alpha=beta line suggests the existence of a nonsaturating state that reduces the stability domain of straight filaments. The results are obtained through extensive simulations of the complex Ginzburg-Landau equation on large domains for long times, in conjunction with simulations on equivalent two-dimensional reductions of this equation and analytical considerations based on topological concepts.