Characterization of nanoporous gold electrodes for bioelectrochemical applications

The high surface areas of nanostructured electrodes can provide for significantly enhanced surface loadings of electroactive materials. The fabrication and characterization of nanoporous gold (np-Au) substrates as electrodes for bioelectrochemical applications is described. Robust np-Au electrodes were prepared by sputtering a gold-silver alloy onto a glass support and subsequent dealloying of the silver component. Alloy layers were prepared with either a uniform or nonuniform distribution of silver and, post dealloying, showed clear differences in morphology on characterization with scanning electron microscopy. Redox reactions under kinetic control, in particular measurement of the charge required to strip a gold oxide layer, provided the most accurate measurements of the total electrochemically addressable electrode surface area, A(real). Values of A(real) up to 28 times that of the geometric electrode surface area, A(geo), were obtained. For diffusion-controlled reactions, overlapping diffusion zones between adjacent nanopores established limiting semi-infinite linear diffusion fields where the maximum current density was dependent on A(geo). The importance of measuring the surface area available for the immobilization was determined using the redox protein, cyt c. The area accessible to modification by a biological macromolecule, A(macro), such as cyt c was reduced by up to 40% compared to A(real), demonstrating that the confines of some nanopores were inaccessible to large macromolecules due to steric hindrances. Preliminary studies on the preparation of np-Au electrodes modified with osmium redox polymer hydrogels and Myrothecium verrucaria bilirubin oxidase (MvBOD) as a biocathode were performed; current densities of 500 μA cm(-2) were obtained in unstirred solutions.     

ChemInform Abstract: Pressure‐Induced Formation of Molecular B2X4(μ‐X)2 (X: Cl,Br, I) Species.

Gas‐phase formation and decomposition of the boron(III) halides of title is explored by CCSD(T) and MP2 ab initio calculations.     

Asymptotic analysis of 3D thin anisotropic plates with a piezoelectric patch

We consider a thin elastic plate with piezo patches mounted on top of it. Electrodes are located on the upper and, depending on the devices, at the lower surface of the patches. This piezo actuator is coupled to an elastic body. We develop an asymptotic procedure to derive a two‐dimensional approximation of the entire structure. As a result, we obtain an inhomogeneous fourth‐order plate equation with piecewise smooth coefficients for the vertical displacement coupled to a second‐order in‐plane problem. The analysis and the resulting asymptotic limits help clarifying the modeling issue concerning active piezo devices in multidimensional smart structures. Copyright © 2012 John Wiley & Sons, Ltd.     

Asymptotics for estimation of quantile regressions with truncated infinite-dimensional processes

Many processes can be represented in a simple form as infinite-order linear series. In such cases, an approximate model is often derived as a truncation of the infinite-order process, for estimation on the finite sample. The literature contains a number of asymptotic distributional results for least squares estimation of such finite truncations, but for quantile estimation, results are not available at a level of generality that accommodates time series models used as finite approximations to processes of potentially unbounded order. Here we establish consistency and asymptotic normality for conditional quantile estimation of truncations of such infinite-order linear models, with the truncation order increasing in sample size. We focus on estimation of the model at a given quantile. The proofs use the generalized functions approach and allow for a wide range of time series models as well as other forms of regression model. The results are illustrated with both analytical and simulation examples.     

Distance sensing using dynamic speckles formed by micro-electro-mechanical-systems deflector

We present a novel architecture of dynamic-speckles distance sensors with a micro-electro-mechanical system (MEMS) deflecting mirror for surface scanning. Since the MEMS mirror deflects the beam sinusoidally, the speed of scanning varies during the scan leading to sufficient variations in the signal frequency which is used to evaluate the distance to the object. Nevertheless, this feature does not affect the accuracy of range measurements when the distance is estimated from zero-crossing counts of the signal during a specially chosen time window within the scan. Experimental results indicate that a single 1 ms scan yields 70 μm accuracy of distance measurement. Averaging data from multiple scans of different surface areas during a 1-s measurement can provide approximately 2 mm of accuracy. Precision of the measurements can be further improved by optimization of the optical system. The compactness of the MEMS deflector and simplicity of the suggested signal processing provides a good basis for practical applications of this distance sensor.     

Graphene Nanobelts,Möbius and Higher Order Möbius Strips Formed from Graphene. A Combined CASSCF/DFT Study

Russian Journal of Physical Chemistry A - Twisted graphene nanoribbons with linking numbers (Lk) of 2 and 3 have been studied at hybrid DFT and CASSCF levels. CASSCF calculations demonstrated...     

Push–pull hyperbranched molecules. A theoretical study

The electronic properties of the ground state, unrelaxed and relaxed first excited states of push–pull hyperbranched molecules bearing amino and nitro terminal groups have been studied at BB1K/cc‐pvdz//HF/6‐31g(d), TD‐BB1K/cc‐pvdz//HF/6‐31g(d) and TD‐BB1K/cc‐pvdz//CIS/6‐31g(d) levels of theory, respectively. It was demonstrated that dendritic architecture of push–pull molecules favours the charge transfer in the excited state compared to linear molecules. The possibility of adopting a plane conformation is an important condition for the charge transfer in an excited state. According to the calculations 1:1 ratio of donor and acceptor groups is another important precondition for the manifestation of strong charge separation in the excited state. In case of excess of nitro groups over the amino, some of the excitations participating in the S0 → S1 transition favour the charge transfer in the excited state in the opposite directions, thus decreasing the charge separation. Copyright © 2008 John Wiley & Sons, Ltd.     

Molecular modelling of hyperbranched polyacetylene

Ab initio and density functional theory calculations carried out on linear and dendritic polyacetylenic (PA) oligomers of different size showed that acetylenic dendrimers are less stable than trans‐PA oligomers and that the instability increases with molecular weight reflecting the strain in crowded hyperbranched structures. However, the energy difference between linear and dendritic structure is rather small and tends to a limit with molecular weight. Twisting of the double bonds decreases the conjugation in hyperbranched PA compared to linear trans‐PA. However, the conjugation though less effective than in trans‐PA is extended up to the 4^th or 5^th generation of dendrimers. It was shown that bromine end groups strongly affect the electronic properties of acetylenic dendrimers decreasing even more the conjugation due to the sterical hindrances, however, highly polarizable bromine atoms reduced significantly the adiabatic potentials of ionization to be very close to that for trans‐PA oligomers.     

Hydrogel composites of neutral and slightly charged poly (acrylamide) gels with incorporated bentonite. Interaction with salt,linear polyelectrolytes and ionic surfactants

The swelling behavior in the solutions of sodium chloride, linear polyelectrolytes and ionic surfactants of the composites based on clay mineral bentonite (BENT) embedded in neutral and slightly charged poly(acrylamide) (PAAm) gels is studied. Negatively charged flat clay particles incorporated into polymer gel adsorb oppositely charged surfactant and linear polyelectrolyte and attract the charged chains of cationic polymer matrix. The results of SAXS study manifest the formation of lamella structure of the cationic surfactant adsorbed by the clay plates. The gels loaded with the clay show a strong response to changes in the nature and the composition of the ionic environment.     

The synthesis of mesogenic polymers provoked by molecular mobility. polysiloxanarylenes

An approach to the synthesis of potentially thermotropic liquid crystalline polymers based on parallel investigation of their molecular mobility was realized. The initial idea was provoked by the observation that there exists some correspondence of molecular mobility data and the ability of a polymer to form a liquid crystalline phase. Previously this phenomenon was demonstrated on the example of a series of thermotropic main chain polymers with flexible dimethylsiloxane spacers of variable length. The relation between the structure of the main chain and local molecular mobility of different fragments was investigated in a series of regular polysiloxane-silarylenes containing rigid aromatic sequences. Molecular mobility was studied by dielectric spectroscopy in solution and in solid state. The structure of the main chain has been changed by variation of the repeated fragments' length, substituents and joint groups. The data of molecular mobility and their conformity with the chain structure were used for directed synthetic search of desired mesogenic polymers.