Palladium-Catalyzed Cross-Coupling of Organozirconium Compounds with Diaryliodonium Salts

The palladium-catalyzed cross-coupling reaction of diaryliodonium salts with organozirconium compounds was achieved for about 1–1.5 hrs at room temperature and the reaction proceeded with retention of configuration to provide a new convenient method for the synthesis of (E)-disubstituted alkenes.     

Shear and extensional rheology of entangled polymer melts: Similarities and differences

This work extends our previous understanding concerning the nonlinear responses of entangled polymer solutions and melts to large external deformation in both simple shear and uniaxial extension. Many similarities have recently been identified for both step strain and startup continuous deformation, including elastic yielding, i.e., chain disentanglement after cessation of shear or extension, and emergence of a yield point during startup deformation that involves a deformation rate in excess of the dominant molecular relaxation rate. At a sufficiently high constant Hencky rate, uniaxial extension of an entangled melt is known to produce window-glass-like rupture. The present study provides evidence against the speculation that chain entanglements tie up into "dead knots" in constant-rate extension because of the exponentially growing chain stretching with time. In particular, it is shown that even Instron-style tensile stretching, i.e., extending a specimen by applying a constant velocity on both ends, results in rupture. Yet, in the same rate range, the same entangled melt only yields in simple shear, and the resulting shear banding is clearly not a characteristic of rupture. Thus, we conclude that chain entanglements respond to simple shear in the manner of yielding whereas uniaxial extension is rather effective in causing some entanglements to lock up, making it impossible for the entanglement network to yield at high rates.     

N-substituted-3(10H)-acridones as visible-light photosensitizers for organic photoredox catalysis

N-Substituted-3(10H)-acridones have been established as visible-light organic photocatalyst. These photosensitizers are efficient for oxidative coupling reaction of N-aryl tetrahydroisoquinolines with various nucleophiles. Notably, N-methyl-3(10H)-acridone (Ia) is stable and can be effectively prepared. It is a water-soluble and atom-economic catalyst, and thus holds promise for green chemical applications. Mechanistic studies confirm a single electron transfer (SET)-induced radical process and a rate-limiting step. Analysis of the photocatalytic reactivity?structure relationship reveals that the acridones are robust and tunable photosensitizers for photoredox catalysis.     

First order optimality conditions for mathematical programs with semidefinite cone complementarity constraints

In this paper we consider a mathematical program with semidefinite cone complementarity constraints (SDCMPCC). Such a problem is a matrix analogue of the mathematical program with (vector) complementarity constraints (MPCC) and includes MPCC as a special case. We first derive explicit formulas for the proximal and limiting normal cone of the graph of the normal cone to the positive semidefinite cone. Using these formulas and classical nonsmooth first order necessary optimality conditions we derive explicit expressions for the strong-, Mordukhovich- and Clarke- (S-, M- and C-)stationary conditions. Moreover we give constraint qualifications under which a local solution of SDCMPCC is a S-, M- and C-stationary point. Moreover we show that applying these results to MPCC produces new and weaker necessary optimality conditions.     

Optimal lower eigenvalue estimates for Hodge-Laplacian and applications

We consider the eigenvalue problem for Hodge-Laplacian on a Riemannian manifold M isometrically immersed into another Riemannian manifold $\overline{M}$. We first assume the pull back Weitzenböck operator of $\overline{M}$ bounded from below, and obtain an extrinsic lower bound for the first eigenvalue of Hodge-Laplacian. As applications, we obtain some rigidity results. Second, when the pull back Weitzenböck operator of $\overline{M}$ bounded from both sides, we give a lower bound of the first eigenvalue by the Ricci curvature of M and some extrinsic geometry. As a consequence, we prove a weak Ejiri type theorem, that is, if the Ricci curvature bounded from below pointwisely by a function of the norm square of the mean curvature vector, then M is a homology sphere. In the end, we give an example to show that all the eigenvalue estimates are optimal when $\overline{M}$ is the space form.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

EFFECTIVE SPECIFIC HEATS OF MULTI-PHASE THERMOELASTIC COMPOSITES

This paper studies the effective properties of multi-phase thermoelastic composites. Based on the Helmholtz free energy and the Gibbs free energy of individual phases, the effective elastic tensor, thermal-expansion tensor, and specific heats of the multi-phase composites are derived by means of the volume average of free-energies of these phases. Particular emphasis is placed on the derivation of new analytical expressions of effective specific heats at constant-strain and constant-stress situations, in which a modified Eshelby’s micromechanics theory is developed and the interaction between inclusions is considered. As an illustrative example, the analytical expression of the effective specific heat for a three-phase thermoelastic composite is presented.