The Density Functional Theory Account of Interplaying Long-Range Exchange and Dispersion Effects in Supramolecular Assemblies of Aromatic Hydrocarbons with Spin

Aromatic hydrocarbons with fused benzene rings and regular triangular shapes, called n-triangulenes according to the number of rings on one edge, form groundstates with n-1 unpaired spins because of topological reasons. Here, we focus on methodological aspects emerging from the density functional theory (DFT) treatments of dimer models of the n = 2 triangulene (called also phenalenyl), observing that it poses interesting new problems to the issue of long-range corrections. Namely, the interaction comprises simultaneous spincoupling and van der Waals effects, i.e., a technical conjuncture not considered explicitly in the benchmarks calibrating long-range corrections for the DFT account of supramolecular systems. The academic side of considering dimer models for calculations and related analysis is well mirrored in experimental aspects, and synthetic literature revealed many compounds consisting of stacked phenalenyl cores, with intriguing properties, assignable to their long-range spin coupling. Thus, one may speculate that a thorough study assessing the performance of state-of-the-art DFT procedures has relevance for potential applications in spintronics based on organic compounds.     

Coordination polymers and a dinuclear complex constructed from zinc(II) ions and fluorescein: iodine adsorption and optical properties

Abstract

1-D coordination polymers, ¹_∞[Zn(fl)₂]·2EtOH and ¹_∞[Zn(fl)₂]·2MeOH, and a dinuclear complex, [{Zn(fl)₂}₂(dienpip)]·4H₂O·4EtOH (dienpip?= N,N′-bis(2-aminoethyl)piperazine), were obtained using Zn(II) ions and fluorescein anions (fl). Thermal analysis shows stability of the polymers after solvent removal up to more than 400?°C. Crystallization solvent molecules were removed under reduced pressure with the preservation of the polymeric structure, ¹_∞[Zn(fl)₂]. Desolvated crystals were exposed to I₂ vapors and the crystal structure determination by X-ray diffraction confirmed the presence of I₂ molecules in the channels generated in crystals by the metal-organic framework. The iodine content, evaluated by X-ray diffraction, corresponds to the overall formula ¹_∞[Zn(fl)₂]·0.3I₂. The optical properties of the coordination polymers and the dinuclear complex have been investigated.     

A linear assignment approach for the least-squares protein morphing problem

This work addresses the computation of free-energy differences between protein conformations by using morphing (i.e., transformation) of a source conformation into a target conformation. To enhance the morphing procedure, we employ permutations of atoms: we seek to find the permutation σ that minimizes the mean-square distance traveled by the atoms. Instead of performing this combinatorial search in the space of permutations, we show that the best permutation can be found by solving a linear assignment problem. We demonstrate that the use of such optimal permutations significantly improves the efficiency of the free-energy computation.     

Boundary behaviour of the mappings satisfying generalized inverse modular inequalities

We study the geometric properties of the mappings for which generalized inverse modular inequalities hold. We generalize in this way known theorems from the theory of analytic mappings and the theory of quasiregular mappings, like the theorems of Fatou, M. and F. Riesz, Beurling and Lindelöf and their extensions given for quasiregular mappings by Martio, Rickman and Vuorinen.     

Tensor product surfaces of euclidean plane curves

Recently B.Y. CHEN initiated the study of the tensor product immersion of two immersions of a given Riemannian manifold [3]. In [6] the particular case of tensor product of two Euclidean plane curves was studied. The minimal one were classified, and necessary and sufficient conditions for such a tensor product to be totally real or complex or slant were established. In the present paper we study for tensor product of Euclidean plane curves the problem of B.Y. CHEN: to what extent do the properties of the tensor product immersion f ? h of two immersions f, h determines the immersions f, h ? [3]     

Fluorescent Flavin/PVP-Coated Silver Nanoparticles: Design and Biological Performance

A red-emitting fluorescent Riboflavin (RF)/Polyvinylpyrrolidone (PVP)-coated silver nanoparticles system, λ_em?=?527 nm, Φ?=?0.242, with a diameter of the metallic core of 27.33 nm and a zeta potential of ? 25.05 mV was prepared and investigated regarding its biological activity. We found that PVP has a key role in RF adsorption around the SNPs surface leading to an enhancement of antioxidant properties (～70%), low cytotoxicity (> 90% cell viability, at 50 µL/mL, after 48 h of incubation) as well as to an efficient process of its cellular uptake (～ 60%, after 24 h of incubation) in L929 cells. The results are relevant concerning the involvement of RF and its coenzymes forms in SNPs - based systems, in cellular respiration as well as for future studies as antioxidant marker system on tumoral cells for viewing and monitoring them, by cellular imaging.

     

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 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     

The number of spanning trees of plane graphs with reflective symmetry

A plane graph is called symmetric if it is invariant under the reflection across some straight line (called symmetry axis). Let G be a symmetric plane graph. We prove that if there is no edge in G intersected by its symmetry axis then the number of spanning trees of G can be expressed in terms of the product of the number of spanning trees of two smaller graphs, each of which has about half the number of vertices of G.