Synthesis and characterization of long perylenediimide polymer fibers: from bulk to the single-molecule level

The synthesis and characterization of perylenediimide polyisocyanides is reported. In addition to short oligomers, our synthetic approach results in the formation of extremely long, well-defined, and rigid perylenediimide polymers. Ordering and close-packing of the chromophores in these long polymers is guaranteed by attachment to a polyisocyanide backbone with amino acid side chains. Hydrogen bonding interactions between those groups stabilize and rigidify the helical polymer structure. The rodlike nature of the synthesized long perylenediimide pendant polyisocyanides as well as the helical arrangement of the chromophores is demonstrated by means of atomic force microscopy. Remarkably, polymer fibers up to 1 mum in length have been visualized, containing several thousands of perylenediimide molecules. Circular dichroism spectroscopy reveals the chiral organization of the chromophore units in the polymer, whereas absorption and emission measurements prove the occurrence of excited-state interactions between those moieties due to the close packing of the chromophore groups. However, an intricate optical behavior is encountered in bulk as a result of the coexistence of short oligomers and long polymers of perylenediimide, a situation subsequently uncovered by means of single-molecule experiments. Individual long helical perylenediimide polyisocyanides exhibit a typical red-shifted fluorescence spectrum, which, together with depolarized emission continuously decreasing in time, demonstrate that fluorescence arises from multiple excimer-like species in the polymer. Upon continuous irradiation of these long polymers, a fast decay in fluorescence lifetime is observed, a situation explained by photoinduced creation of quenching sites. Radical/ion formation by intramolecular electron transfer between close-by perylenediimide moieties is the most probable mechanism for this process. Appropriate control of the electron-transfer process might open the possibility of applying these polymers as perylenediimide-based supramolecular nanowires.     

Conformational features of an actuator containing calix[4]arene and thiophene: a molecular dynamics study

Molecular dynamics simulations have been performed for poly(calix[4]arene bis(bithiophene)) in dichloromethane solution. This material responds to its electronic structure variations with significant conformational changes, producing contraction-expansion movements. Simulations have been performed for the three states of this molecular actuator (reduced, oxidized-nondeprotonated, and oxidized-deprotonated), a specific force-field being developed for each case. Results, which are fully consistent with previous ab initio quantum mechanical calculations on an isolated actuating unit, have revealed important findings about the dynamics of the system. Analyses of the flexibility/rigidity of the molecular chain with the state, the interaction of the polymer with the solvent molecules and the influence of environmental factors (as the viscosity of solvent, the counterions and the thermal agitation) on the dynamics have provided important insights to the actuation mechanism.     

Stereodivergent syntheses of conduramines and aminocyclitols

[reaction: see text] The diastereomers of 6-amino-cyclohex-3-ene-1,2-diols 1 (4-deoxy-3-conduramines), key building blocks for the syntheses of a large range of natural products, have been enantioselectively prepared. Diastereoselective dihydroxylation of the compounds provided a new family of aminocyclitols 2 (deoxyinosamines). The key reactions of our syntheses are Sharpless catalytic asymmetric epoxidation, diastereoselective addition of vinylmetal reagents to the aldehydes, and ring-closing metathesis (RCM).     

Sample entropy of ECG time series of fearful flyers: preliminary results

Research within the framework of the nonlinear dynamical systems (NDS) in the field of anxiety disorders has shown that greater irregularity/complexity appears in the output from healthy systems. In this study we measured the Heart rate variability (HRV) and the sample sntropy (SampEn) of the ECG mV time series of fearful flyers (N = 15) and a matched control group (N = 15) when confronted with three combinations of feared stimuli (pictures, sounds, and pictures with sounds) as well as relaxing stimuli (pictures and sounds). Fearful flyers had lower SampEn than controls in all conditions, including baseline. Non-phobics showed significant entropy decreases from baseline in two out of three exposure conditions. No differences on HRV were found between groups, and HRV was not sensitive to condition changes. The main finding of the study is that the SampEn calculated on very short ECG mV recordings (10 to 60 seconds, easy to obtain in clinical settings) may be a useful diagnostic measure since it can distinguish fearful from non-fearful flyers.     

Generation of light in media with a random distribution of nonlinear domains

We show that the second order nonlinear generation of light, a process that it is assumed to require highly ordered materials, is also possible in structures of randomly oriented nonlinear domains. We explain theoretically why in such disordered structures the efficiency of the nonlinear generation of light grows linearly with the number of domains. Moreover, a higher degree of disorder, obtained when the dispersion is made very large, has no negative effect for the nonlinear light generation. In such conditions, light generation is shown to be equally efficient for any average size of the domains and also to grow linearly with respect to the number of domains.     

Existence, uniqueness, and convergence of the regularized primal-dual central path

In a recent work [J. Castro, J. Cuesta, Quadratic regularizations in an interior-point method for primal block-angular problems, Mathematical Programming, in press (doi:10.1007/s10107-010-0341-2)] the authors improved one of the most efficient interior-point approaches for some classes of block-angular problems. This was achieved by adding a quadratic regularization to the logarithmic barrier. This regularized barrier was shown to be self-concordant, thus fitting the general structural optimization interior-point framework. In practice, however, most codes implement primal-dual path-following algorithms. This short paper shows that the primal-dual regularized central path is well defined, i.e., it exists, it is unique, and it converges to a strictly complementary primal-dual solution.     

ChemInform Abstract: X2Y2 Isomers: Tuning Structure and Relative Stability Through Electronegativity Differences (X: H,Li, Na,F, Cl,Br, I; Y: O,S, Se,Te).

Density functional calculations on XYYX and X₂YY isomers of the X₂Y₂ species (X: H, Li, Na, F, Cl, Br, I; Y: O, S, Se, Te) show that the XYYX isomers are more stable than the X₂YY forms except for X = F and Y = S and Te, for which the F₂SS and F₂TeTe isomers are slightly more stable.     

Schatten classes of integration operators on Dirichlet spaces

We address the problem of determining membership in Schatten-Von Neumann ideals S _p of integration operators (T _g f)(z) = ∫ ₀ ^z = ∫ ₀ ^z f(ξ)g′(ξ)dξ acting on Dirichlet type spaces. We also study this problem for multiplication, Hankel and Toeplitz operators. In particular, we provide an extension of Luecking's result on Toeplitz operators [10, p. 347].     

An enumeration procedure for the assembly line balancing problem based on branching by non-decreasing idle time

In this article, we present a new exact algorithm for solving the simple assembly line balancing problem given a determined cycle time (SALBP-1). The algorithm is a station-oriented bidirectional branch-and-bound procedure based on a new enumeration strategy that explores the feasible solutions tree in a non-decreasing idle time order. The procedure uses several well-known lower bounds, dominance rules and a new logical test based on the assimilation of the feasibility problem for a given cycle time and number of stations (SALBP-F) to a maximum-flow problem.