A Combined Experimental and Computational Study of Chrysanthemin as a Pigment for Dye-Sensitized Solar Cells

The theoretical study of chrysanthemin (cyanidin 3-glucoside) as a pigment for TiO₂-based dye-sensitized solar cells (DSSCs) was performed with the GAUSSSIAN 09 simulation. The electronic spectra of neutral and anionic chrysanthemin molecules were calculated by density functional theory with B3LYP functional and DGDZVP basis set. A better energy level alignment was found for partially deprotonated molecules of chrysanthemin, with the excited photoelectron having enough energy in order to be transferred to the conduction band of TiO₂ semiconductor in DSSCs. In addition, we used the raw aqueous extracts of roselle (Hibiscus sabdariffa) calyces as the source of chrysanthemin and the extracts with various pH values were tested in DSSCs. The extracts and photosensitized semiconductor layers were characterized by UV-Vis spectroscopy, and DSSCs based on raw extracts were characterized by current density-voltage measurements.     

Metal-Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S-Oxides

Benzothiophenes, activated by oxidation to the corresponding S-oxides, undergo C−H/C−H-type coupling with phenols to give C4 arylation products. While an electron-withdrawing group at C3 of the benzothiophene is important, the process operates without a directing group and a metal catalyst, thus rendering it compatible with sensitive functionalities—e.g. halides and formyl groups. Quantum chemical calculations suggest a formal stepwise mechanism involving heterolytic cleavage of an aryloxysulfur species to give a π-complex of the corresponding benzothiophene and a phenoxonium cation. Subsequent addition of the phenoxonium cation to the C4 position of the benzothiophene is favored over the addition to C3; Fukui functions predict that the major regioisomer is formed at the more electron-rich position between C3 and C4. Varied selective manipulation of the benzothiophene products showcase the synthetic utility of the metal-free arylation process.     

A Variational Characterization of the Effective Yield Set for Ionic Polycrystals

The effective yield set of ionic polycrystals is characterized by means of variational principles in $L^\infty $ associated to supremal functionals acting on matrix-valued divergence-free fields.     

Parallel distributed-memory simplex for large-scale stochastic LP problems

We present a parallelization of the revised simplex method for large extensive forms of two-stage stochastic linear programming (LP) problems. These problems have been considered too large to solve with the simplex method; instead, decomposition approaches based on Benders decomposition or, more recently, interior-point methods are generally used. However, these approaches do not provide optimal basic solutions, which allow for efficient hot-starts (e.g., in a branch-and-bound context) and can provide important sensitivity information. Our approach exploits the dual block-angular structure of these problems inside the linear algebra of the revised simplex method in a manner suitable for high-performance distributed-memory clusters or supercomputers. While this paper focuses on stochastic LPs, the work is applicable to all problems with a dual block-angular structure. Our implementation is competitive in serial with highly efficient sparsity-exploiting simplex codes and achieves significant relative speed-ups when run in parallel. Additionally, very large problems with hundreds of millions of variables have been successfully solved to optimality. This is the largest-scale parallel sparsity-exploiting revised simplex implementation that has been developed to date and the first truly distributed solver. It is built on novel analysis of the linear algebra for dual block-angular LP problems when solved by using the revised simplex method and a novel parallel scheme for applying product-form updates.     

Fixed point results on a metric space endowed with a finite number of graphs and applications

In this paper, we consider self-mappings defined on a metric space endowed with a finite number of graphs. Under certain conditions imposed on the graphs, we establish a new fixed point theorem for such mappings. The obtained result extends, generalizes and improves many existing contributions in the literature including standard fixed point theorems, fixed point theorems on a metric space endowed with a partial order and fixed point theorems for cyclic mappings.     

An existence result for a nonhomogeneous problem in R2 related to nonlinear Hencky-type materials

This paper investigates a nonlinear and non-homogeneous system of partial differential equations. The motivation comes from the fact that in a particular case the problem discussed here can be used in modeling the behavior of nonlinear Hencky-type materials. The main result of the paper establishes the existence of a nontrivial solution in an adequate functional space of Orlicz–Sobolev type by using Schauder’s fixed point theorem combined with adequate variational techniques.     

On hermitian polynomial optimization

We compare three levels of algebraic certificates for evaluating the maximum modulus of a complex analytic polynomial, on a compact semi-algebraic set. They are obtained as translations of some recently discovered inequalities in operator theory. Although they can be stated in purely algebraic terms, the only known proofs for these decompositions have a transcendental character. Received: 27 June 2005     

Matrix Representations for Positive Noncommutative Polynomials

In real semialgebraic geometry it is common to represent a polynomial q which is positive on a region R as a weighted sum of squares. Serious obstructions arise when q is not strictly positive on the region R. Here we are concerned with noncommutative polynomials and obtaining a representation for them which is valid even when strict positivity fails. Specifically, we treat a ``symmetric' polynomial q(x, h) in noncommuting variables, {x<sub>1</sub>, . . . , } and {h<sub>1</sub>, . . . , } for which q(X,H) is positive semidefinite whenever are tuples of selfadjoint matrices with ||X<sub>j</sub>|| ≤ 1 but H<sub>j</sub> unconstrained. The representation we obtain is a Gram representation in the variables h where P<sub>q</sub> is a symmetric matrix whose entries are noncommutative polynomials only in x and V is a ``vector' whose entries are polynomials in both x and h. We show that one can choose P_q such that the matrix P_q(X) is positive semidefinite for all ||X_j|| ≤ 1. The representation covers sum of square results ([Am. Math. (to appear); Linear Algebra Appl. 326 (2001), 193–203; Non commutative Sums of Squares, preprint]) when g_x = 0. Also it allows for arbitrary degree in h, rather than degree two, in the main result of [Matrix Inequalities: A Symbolic Procedure to Determine Convexity Automatically to appear IOET July 2003] when restricted to x-domains of the type ||X_j|| ≤ 1. Partially supported by NSF, DARPA and Ford Motor Co. Partially supported by NSF grant DMS-0140112 Partially supported by NSF grant DMS-0100367     

On the classification of complex vector bundles of stable rank

One describes, using a detailed analysis of Atiyah-Hirzebruch spectral sequence, the tuples of cohomology classes on a compact, complex manifold, corresponding to the Chern classes of a complex vector bundle of stable rank. This classification becomes more effective on generalized flag manifolds, where the Lie algebra formalism and concrete integrability conditions describe in constructive terms the Chern classes of a vector bundle. Since deceased.