Photoinduced charge carrier dynamics of Zn-porphyrin-TiO2 electrodes: the key role of charge recombination for solar cell performance

Time resolved absorption spectroscopy has been used to study photoinduced electron injection and charge recombination in Zn-porphyrin sensitized nanostructured TiO(2) electrodes. The electron transfer dynamics is correlated to the performance of dye sensitized solar cells based on the same electrodes. We find that the dye/semiconductor binding can be described with a heterogeneous geometry where the Zn-porphyrin molecules are attached to the TiO(2) surface with a distribution of tilt angles. The binding angle determines the porphyrin-semiconductor electron transfer distance and charge transfer occurs through space, rather than through the bridge connecting the porphyrin to the surface. For short sensitization times (1 h), there is a direct correlation between solar cell efficiency and amplitude of the kinetic component due to long-lived conduction band electrons, once variations in light harvesting (surface coverage) have been taken into account. Long sensitization time (12 h) results in decreased solar cell efficiency because of decreased efficiency of electron injection.     

Attachment of a Hydrogen‐Bonding Carboxylate Side Chain to an [FeFe]‐Hydrogenase Model Complex: Influence on the Catalytic Mechanism

Azapropanedithiolate (adt)‐bridged model complexes of [FeFe]‐hydrogenase bearing a carboxylic acid functionality have been designed with the aim of decreasing the potential for reduction of protons to hydrogen. Protonation of the bisphosphine complexes 4 – 6 has been studied by in situ IR and NMR spectroscopy, which revealed that protonation with triflic acid most likely takes place first at the N‐bridge for complex 4 but at the Fe? Fe bond for complexes 5 and 6 . Using an excess of acid, the diprotonated species could also be observed, but none of the protonated species was sufficiently stable to be isolated in a pure state. Electrochemical studies have provided an insight into the catalytic mechanisms under strongly acidic conditions, and have also shown that complexes 3 and 6 are electro‐active in aqueous solution even in the absence of acid, presumably due to hydrogen bonding. Hydrogen evolution, driven by visible light, has been observed for three‐component systems consisting of [Ru(bpy)₃]²⁺, complex 1 , 2 , or 3 , and ascorbic acid in CH₃CN/D₂O solution by on‐line mass spectrometry.     

Ergodic,primal convergence in dual subgradient schemes for convex programming,II: the case of inconsistent primal problems

Consider the utilization of a Lagrangian dual method which is convergent for consistent convex optimization problems. When it is used to solve an infeasible optimization problem, its inconsistency will then manifest itself through the divergence of the sequence of dual iterates. Will then the sequence of primal subproblem solutions still yield relevant information regarding the primal program? We answer this question in the affirmative for a convex program and an associated subgradient algorithm for its Lagrange dual. We show that the primal–dual pair of programs corresponding to an associated homogeneous dual function is in turn associated with a saddle-point problem, in which—in the inconsistent case—the primal part amounts to finding a solution in the primal space such that the Euclidean norm of the infeasibility in the relaxed constraints is minimized; the dual part amounts to identifying a feasible steepest ascent direction for the Lagrangian dual function. We present convergence results for a conditional \(\varepsilon \)-subgradient optimization algorithm applied to the Lagrangian dual problem, and the construction of an ergodic sequence of primal subproblem solutions; this composite algorithm yields convergence of the primal–dual sequence to the set of saddle-points of the associated homogeneous Lagrangian function; for linear programs, convergence to the subset in which the primal objective is at minimum is also achieved.     

Material property estimates from ultrasound attenuation in fibre suspensions

An investigation of a new method for measuring fibre material properties from ultrasonic attenuation in a dilute suspension of synthetic fibres of uniform geometry is presented. The method is based on inversely solving an ultrasound scattering and absorption model of suspended fibres in water for the material properties of the fibres. Experimental results were obtained from three suspensions of nylon 66 fibres each with different fibre diameters. A forward solution to the model with reference material values is compared to experimental data to verify the model’s behaviour. Estimates of the shear and Young’s modulus, the compressional wave velocity, Poisson’s ratio and loss tangent from nylon 66 fibres are compared to data available from other sources. Experimental data confirms that the model successfully predicts that the resonance features in the frequency response of the attenuation are a function of diameter. Consistent estimated values for the compressional wave velocity and the Poisson’s ratio were found to be difficult to obtain but in combination gave values of shear modulus within previously reported values and with low sensitivity to noise. Young’s modulus was underestimated by 54% but was consistent and had low sensitivity to noise. The underestimation is believed to be caused by the assumption of isotropic material used in the model. Additional tests on isotropic fibre would confirm this. Further analysis of the model sensitivity and the reasons for the resonance features are required.     

On boundary layers

The concept of boundary layers, introduced by A. Volberg in [7], is generalized from subsets of the unit disk to subsets of general non-tangentially accessible (NTA) domains. Capacitary conditions of Wiener type series of both necessary and sufficient type for boundary layers are presented and the connection between boundary layers and minimally thin sets is studied.     

Flexible composites, strength, deformation, and fracture processes. 1. Reinforcement structures and tensile strength

Fiber-reinforced flexible composites are extensively used for different kinds of applications, for example, tubes, drive belts, tires, and coated fabrics. Typical for these materials are matrix materials allowing large strain deformation and reinforcement structures allowing bending. Apart from the tensile strength and limited bending stiffness, damage resistance and ductile-brittle transition characteristics are discussed. The tensile strength usually follows the rule of mixture. The mode of fracture and damage resistance, however, strongly depend on penetration of the matrix into the fiber bundles, textile structure, and internal friction. Models for the work of fracture and the ductile-to-brittle fracture transition are discussed.Presented at the 10th International Conference on the Mechanics of Composite Materials (Riga, April 20–23, 1998).Published in Mekhanika Kompozitnykh Materialov, Vol. 34, No. 6, pp. 747–760, November–December, 1998.     

Adaptive first integral preserving methods for PDEs

We present a method for constructing first integral preserving numerical schemes for time-dependent partial differential equations on non-uniform grids, using a finite difference approach for spatial discretization and discrete gradients for time stepping. The method is extended to accommodate spatial adaptivity. A numerical experiment is carried out where the method is applied to the Sine-Gordon equation with moving mesh adaptivity. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of an Orthogonal Topological Analogue of Helicene

The synthesis of an orthogonal topological pentamer analogue of helicene is presented. This analogue forms a tubular structure with its aromatic systems directed parallel to the axis of propagation, which creates a cavity with the potential to function as a host molecule. The synthetic strategy reported, based on a series of repeating Friedländer condensations that utilize pyrido[3,2‐d]pyrimidine moieties as protected amino aldehydes, allows for the facile access of higher generations of helical, tubular structures. As a result of the synthetic strategy, only a helical isomer of the pentamer is possible. The structure and absolute configuration of the pentamer were elucidated from a combination of NMR spectroscopic data, optical properties, X‐ray structures, and by comparison of an experimental electronic circular dichroism spectrum to a calculated spectrum.     

Alkyl chain order in a lamellar lyotropic liquid crystal with varying surface charge density

Abstract

The alkyl chain order in the lamellar liquid-crystalline phase formed in the octylamine/octylammonium chloride/water system has been investigated by ²H N.M.R. at constant mole ratio water/amphiphile and varying charge of the lamellae. The results are correlated to the dimensions of the aggregate obtained from X-ray low angle diffraction measurements.