Light harvesting and efficient energy transfer in a boron-dipyrrin (BODIPY) functionalized perylenediimide derivative

[reaction: see text] Click chemistry has been successfully applied in the synthesis of a bay region tetraboron-dipyrrin (BODIPY) appended perylenediimide (PDI). This light-harvesting molecule presents a large cross section for the absorption of light in the visible region. Excitation energy is efficiently channeled to the perylenediimide core. This novel antenna system is the first demonstration of the efficiency of energy transfer in a BODIPY-PDI bichromophoric system and appears to be highly promising for the design and synthesis of similar dendritic structures.     

Ionic conductivity of PVdF-co-HFP/LiClO4 in terms of free volume defects probed by positron annihilation lifetime spectroscopy

ABSTRACT

Polymers based on ionic conducting materials have important interest because of their potential applications in polymer electrolytes and membranes for fuel cell application. PVdF-co-HFP poly(viniliden-co-hexafluoropropylene) was chosen as a polymer matrix because of its high ionic conductivity and better mechanical properties. Polymer matrix composites were prepared with various amounts of LiClO₄ salt by a solution casting method. The sample-ionic conductivity measurements were recorded by AC impedance analyzer at different frequencies from 0.1?Hz to 20?MHz and at different temperatures from 273 to 373?K.

The changes of nanoscopic free volume and free volume fraction in these materials were investigated in terms of temperature from 273 to 373?K using Positron Annihilation Lifetime Spectroscopy (PALS) and Simha-Somcynsky (SS) Hole Theory. The free volume had a bump at about 3% in weight percentage of the salt and there is a slight increase after 10%. The effects of weight percentages of LiClO₄ and temperature were investigated. The mechanism of the ac ionic conductivity was presented in terms of the free volume models, however thermo-occupancy function justifies the best accurate representation of the data.     

A landing theorem for periodic dynamic rays for transcendental entire maps with bounded post-singular set

In this article, we present a landing theorem for periodic dynamic rays for transcendental entire maps which have bounded post-singular sets, by using standard hyperbolic geometry results.     

Multi-location transshipment problem with capacitated production

We consider coordination among stocking locations through replenishment strategies that explicitly take into account lateral transshipments, i.e., transfer of a product among locations at the same echelon level. Our basic contribution is the incorporation of supply capacity into the traditional transshipment model. Our goal is to analyze the impact on system behavior and on stocking locations’ performance of the fact that the supplier may fail to fulfill all the replenishment orders. We therefore formulate the capacitated supply scenario as a network flow problem embedded in a stochastic optimization problem, which is solved through a sample average approximation method. We find that, depending on the production capacity, system behavior can vary drastically. Moreover, in a production-inventory system, we find evidence that either capacity flexibility (i.e., extra production) or transshipment flexibility (i.e., pooling) is required to maintain a desired level of service.     

Novel C2-symmetric macrocycles bearing diamide-diester groups: synthesis and enantiomeric recognition for primary alkyl ammonium salts

We synthesized a series of novel macrocycles with diamide-diester groups (S,S)-1, (S,S)-2, (S,S)-3, and (R,R)-1, derived from dimethyloxalate and amino alcohols by high dilution technique, and evaluated enantiomeric recognition properties of these macrocycles toward primary alkyl ammonium salts by 1H NMR titration. Taking into account the host employed, important differences were observed in the Ka values of (R)-Am and (S)-Am for (S,S)-1 and (R,R)-1 hosts, KS/KR = 5.55 and KR/KS = 3.65, Delta Delta Go = 0.43 and -0.32 kJ mol-1, respectively. There seems a general tendency for the host to include the guests with the same absolute configuration.     

Laccase-based amperometric biosensor enhanced by Ni/Au/PPy-COOH multisegmental nanowires for selective dopamine detection

One-dimensional Ni/Au/PPy-COOH nanowires with multiple segments were synthesized in this study. Smooth surfaces and magnetic properties of nanowires were investigated by scanning transmission electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDX), and Electron Spin Resonance (ESR) techniques. The nanowires were used to modify the screen-printed electrode surface and as a micro-environment for Trametes versicolor laccase. The ability of this enzyme biosensor to detect dopamine change in human biological samples was demonstrated by a wide linear range (0.01–50 μM) and a low LOD (2.265 nM). In addition, the biosensor exhibited excellent selectivity allowing the detection of dopamine in the presence of ascorbic acid, uric acid, L-Cys, serotonin, and glucose, with high sensitivity of reduction currents obtained at −0.2 V (vs. Ag/AgCl). The proposed biosensor allowed the detection of dopamine in commercial serum and artificial urine with recovery values close to 100 %. It also demonstrated reproducibility, reusability, and long-term storage stability. The sensitivity, K_m^app, and I_max values of the biosensor were determined as 2.05 μM and 1.03 μA, respectively. The LAC-Ni/Au/PPy-COOH/NAF/SPE biosensor is a reliable design for detecting dopamine with a wide linear range.     

Simulating electron spin resonance spectra of nitroxide spin labels from molecular dynamics and stochastic trajectories

Simulating electron spin resonance spectra of nitroxide spin labels from motional models is necessary for the quantitative analysis of experimental spectra. We present a framework for modeling the spin label dynamics by using trajectories such as those from molecular dynamics (MD) simulations combined with stochastic treatment of the global protein tumbling. This is achieved in the time domain after two efficient numerical integrators are developed: One for the quantal dynamics of the spins and the other for the classical rotational diffusion. For the quantal dynamics, we propagate the relevant part of the spin density matrix in Hilbert space. For the diffusional tumbling, we work with quaternions, which enables the treatment of anisotropic diffusion in a potential expanded as a sum of spherical harmonics. Time-averaging arguments are invoked to bridge the gap between the smaller time step of the MD trajectories and the larger time steps appropriate for the rotational diffusion and/or quantal spin dynamics.     

On the Modeling of CO2 EUA and CER Prices of EU‐ETS for the 2008–2012 Period

Increased consumption of fossil fuels in industrial production has led to a significant elevation in the emission of greenhouse gases and to global warming. The most effective international action against global warming is the Kyoto Protocol, which aims to reduce carbon emissions to desired levels in a certain time span. Carbon trading is one of the mechanisms used to achieve the desired reductions. One of the most important implications of carbon trading for industrial systems is the risk of uncertainty about the prices of carbon allowance permits traded in the carbon markets. In this paper, we consider stochastic and time series modeling of carbon market prices and provide estimates of the model parameters involved, based on the European Union emissions trading scheme carbon allowances data obtained for 2008–2012 period. In particular, we consider fractional Brownian motion and autoregressive moving average–generalized autoregressive conditional heteroskedastic modeling of the European Union emissions trading scheme data and provide comparisons with benchmark models. Our analysis reveals evidence for structural changes in the underlying models in the span of the years 2008–2012. Data‐driven methods for identifying possible change‐points in the underlying models are employed, and a detailed analysis is provided. Our analysis indicated change‐points in the European Union Allowance (EUA) prices in the first half of 2009 and in the second half of 2011, whereas in the Certified Emissions Reduction (CER) prices three change‐points have appeared, in the first half of 2009, the middle of 2011, and in the second half of 2012. These change‐points seem to parallel the global economic indicators as well. Copyright © 2016 John Wiley & Sons, Ltd.