Influence of aggregates and solvent aromaticity on the emission of conjugated polymers

The influence of aggregates and solvent aromaticity on the photophysics and fluorescence dynamics of two conjugated polymers is studied. The two polymers are derivatives of poly(p-phenylene vinylene) (PPV) containing different kinked moieties along the main chain. The polymers contain 2,6-diphenylpyridine and m-terphenyl kinked moieties and they are abbreviated as PN and PC, respectively. The insertion of kinked segments along the main chain shifts the emission spectrum from the yellow-orange spectral region, common to PPV derivatives, to the blue-green spectral region. The results show that in dilute solutions the polymers decay monoexponentially, while in concentrated ones the fluorescence decays biexponentially, indicating fluorescence quenching. This is attributed to an energy transfer process from polymer chains to aggregates that occurs within a few tens of picoseconds. By comparing the photophysics and fluorescence dynamics of polymer PN in a nonaromatic and an aromatic solvent, we conclude that the polymer conformation adopted in the aromatic solvent leads to a higher fluorescence quantum yield and a longer fluorescence lifetime. Furthermore, the fluorescence quenching of PN because of aggregates is faster and more efficient in the aromatic than in the nonaromatic solvent. These results can be explained through a more extended chain conformation of PN in the aromatic solvent.     

Femtosecond time resolved fluorescence dynamics of a cationic water-soluble poly(fluorenevinylene-co-phenylenevinylene)

A recently synthesized cationic water-soluble poly(fluorenevinylene-co-phenylenevinylene) was studied by means of steady state and femtosecond time resolved upconversion spectroscopy in aqueous and EtOH solutions. Steady state spectroscopic measurements showed that the polymer emits at the blue-green spectral region and that aggregates are formed in concentrated polymer solutions. The fluorescence dynamics of the polymer in concentrated solutions, studied at a range of emission wavelengths, exhibited a wavelength dependent and multiexponential decay, indicating the existence of various decay mechanisms. Specifically, a rapid decay at short emission wavelengths and a slow rise at long wavelengths were observed. Both features reveal an energy transfer process from isolated to aggregated chains. The contribution of the energy transfer process as well as of the isolated chains and the aggregates on the overall fluorescence decay of the polymer was determined. The dependence of the energy transfer rate and efficiency on polymer concentration was also examined.     

A descent hybrid conjugate gradient method based on the memoryless BFGS update

In this work, we present a new hybrid conjugate gradient method based on the approach of the convex hybridization of the conjugate gradient update parameters of DY and HS+, adapting a quasi-Newton philosophy. The computation of the hybrization parameter is obtained by minimizing the distance between the hybrid conjugate gradient direction and the self-scaling memoryless BFGS direction. Furthermore, a significant property of our proposed method is that it ensures sufficient descent independent of the accuracy of the line search. The global convergence of the proposed method is established provided that the line search satisfies the Wolfe conditions. Our numerical experiments on a set of unconstrained optimization test problems from the CUTEr collection indicate that our proposed method is preferable and in general superior to classic conjugate gradient methods in terms of efficiency and robustness.     

Control policies for single-stage production systems with perishable inventory and customer impatience

We consider problems of inventory and admission control for make-to-stock production systems with perishable inventory and impatient customers. Customers may balk upon arrival (refuse to place orders) and renege while waiting (withdraw delayed orders) during stockouts. Item lifetimes and customer patience times are random variables with general distributions. Processing, setup, and customer inter-arrival times are however assumed to be exponential random variables. In particular, the paper studies two models. In the first model, the system suspends its production when its stock reaches a safety level and can resume later without incurring any setup delay or cost. In the second model, the system incurs setup delays and setup costs; during stockouts, all arriving customers are informed about anticipated delays and either balk or place their orders but cannot withdraw them later. Using results from the queueing literature, we derive expressions for the system steady-state probabilities and performance measures, such as profit from sales and costs of inventory, setups, and delays in filling customer orders. We use these expressions to find optimal inventory and admission policies, and investigate the impact of product lifetimes and customer patience times on system performance.     

Derivation and evaluation of the fourth moment of NMR lineshape in zero-field

An expression for the fourth moment in zero-field NMR has been analytically derived and numerically evaluated for a rigid cubic lattice. Model simulations have been performed to calculate the second moment, the fourth moment, the ratio of the fourth moment to the square of the second moment, and the width of the resonance line for a crystal and a polycrystalline material in high-field as well as in zero-field NMR. The simulation results allow us to draw two conclusions: (1) zero-field NMR gives sharper and better defined spectra than the high-field NMR and (2) the ratio of the high- to zero-field resonance line-widths is 4 for a crystal, whereas it is 11 for a polycrystalline material.     

Convergence rate of inertial Forward–Backward algorithm beyond Nesterov’s rule

Mathematical Programming - In this paper we study the convergence of an Inertial Forward–Backward algorithm, with a particular choice of an over-relaxation term. In particular we show that...     

Magnetically modified single and turbostratic stacked graphenes from tris(2,2'-bipyridyl) iron(II) ion-exchanged graphite oxide

Loading of graphite oxide (GO) with tris(2,2'-bipyridyl) iron(II) ions and subsequent calcination affords a novel graphene-based composite with magnetic and electrically conductive properties. The pH of the starting aqueous suspension and the washing procedure play a crucial role in the successful immobilization of the iron precursor, which is mainly governed by ion exchange. The complex is intercalated between the graphene oxide layers, where it adopts a distorted conformation. Rapid heating of this solid results in the deflagration of GO and the formation of ultrafine ( d = 2-14 nm) Fe2O3 particles with maghemite as the dominant phase. The superparamagnetic maghemite crystals are dispersed uniformly in the high-surface-area diamagnetic matrix built up from single or turbostratic stacked graphenes.     

Salicylaldoxime in manganese(III) carboxylate chemistry: Synthesis, structural characterization and physical studies of hexanuclear and polymeric complexes

The use of salicylaldehyde oxime (H₂salox) in manganese(III) carboxylate chemistry has yielded new members of the family of hexanuclear compounds presenting the [Mn₆(μ₃-O)₂(μ₂-OR)₂]¹²⁺ core, complexes [Mn^III₆(μ₃-O)₂(O₂CPh)₂(salox)₆(L₁)₂(L₂)₂] (L₁ = py, L₂ = H₂O (1); L₁ = Me₂CO, L₂ = H₂O (2); L₁ = L₂ = MeOH (3)). Addition of NaOMe to the acetonitrile reaction mixture, afforded the 1D complex [Mn^III₃Na(μ₃-O)(O₂CPh)₂(salox)₃(MeCN)]_n (4), whereas addition of NaClO₄ to the acetone reaction mixture afforded an analogous 1D complex [Mn^III₃Na(μ₃-O)(O₂CPh)₂(salox)₃(Me₂CO)]_n (5). The structures of 1–3 present the [Mn₆(μ₃-O)₂(μ₂-OR)₂]¹²⁺ core and can be described as two [Mn₃(μ₃-O)]⁷⁺ triangular subunits linked by two μ₂-oximato oxygen atoms of the salox²⁻ ligands, which show the less common μ₃-κ²O:κO′:κN coordination mode. The benzoato ligands are coordinated through the usual syn,syn-μ₂-κO:κO′ mode. The 1D polymeric structures of 4 and 5 consist of alternating [Mn₃(μ₃-O)]⁷⁺ subunits and Na⁺ atoms linked through two μ₃-κ²O:κO′:κN and one μ₄-κ²O:κ²O′:κN salox²⁻ ligands as well as one syn,anti-μ₂-κO:κO′ benzoato ligand. DC and AC magnetic susceptibility studies on 1 revealed the stabilization of an S = 4 ground state, and indications of single-molecule magnetism behavior, whereas the DC experimental data from polycrystalline sample of 5 are indicative of antiferromagnetic interactions within the [Mn₃] subunit. Solid state ¹H NMR data of 1 were used to probe the spin-lattice relaxation of the system.     

Acetate/di-2-pyridyl ketone oximate "blend" as a source of high-nuclearity nickel(II) clusters: dependence of the nuclearity on the nature of the inorganic anion present

The use of di-2-pyridyl ketone oxime [(py)2CNOH] in reactions with Ni(O2CMe)2.4H2O, in the presence or absence of extra inorganic anions (N3- and SCN-) has led to Ni4, Ni5, and Ni7 clusters; the magnetic study of the heptanuclear nickel(II) complex reveals an S = 3 ground state.