An Enzyme‐free H2O2 Sensor Based on Poly(2‐Aminophenylbenzimidazole)/Gold Nanoparticles Coated Pencil Graphite Electrode

A poly(2‐aminophenylbenzimidazole)/gold nanoparticles (P2AB/AuNPs) coated disposable pencil graphite electrode (PGE) was fabricated as an enzyme‐free sensor for the H₂O₂ determination. P2AB/AuNPs and P2AB were successfully synthesized electrochemically on PGE in acetonitrile for the first time. The coatings were characterized by scanning electron microscopy, X‐ray diffraction spectroscopy, Energy‐dispersive X‐ray spectroscopy, Surface‐enhanced Raman spectroscopy, and UV‐Vis spectroscopy. AuNPs interacted with P2AB as carrier enhances the electrocatalytic activity towards reduction of H₂O₂. The analytical performance was evaluated in a 100 mM phosphate buffer solution at pH 6.5 by amperometry. The steady state current vs. H₂O₂ concentration is linear in the range of 0.06 to 100 mM (R²=0.992) with a limit of detection 3.67×10^?5 M at ?0.8 V vs. SCE and no interference is caused by ascorbic acid, dopamine, uric acid, and glucose. The examination for the sensitive determination of H₂O₂ was conducted in commercially available hair oxidant solution. The results demonstrate that P2AB/AuNPs/PGE has potential applications as a sensing material for quantitative determination of H₂O₂.     

Molecular depth profiling of polymers with very low energy ions

The need for a molecular depth profiling technique to study organic layers has become a strong incentive in the SIMS community in the last few years, especially with the recent successes obtained with cluster ion beam depth profiling. In this work, we have investigated a thoroughly different approach by using very low energy (down to 200 eV) monoatomic or diatomic ions to sputter organic matter. Quite surprisingly, we were able to retain specific molecular information on various polymers even at very high fluence.Polymethylmethacrylate (PMMA) and polyethylene terephthalate (PET) films were depth-profiled with 200 eV Cs⁺ and 500 eV O₂⁺ ions. With 200 eV Cs ions, the best profiles were obtained in the negative mode, due to a strong negative ionisation yield enhancement related to Cs retention in the polymer. A relatively high and stable signal from the most characteristic ions was measured all over the layer.With 500 eV O₂⁺, real molecular depth-profiles were also obtained in both the positive and the negative modes. Once again, the main characteristic fragments of PET or PMMA remain detectable with stable yields all over the profile.     

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.     

Revised model core potentials of s-block elements

We developed new model core potentials (MCPs) for s-block elements from Na to Ra, in which the outer core (n-1)s and (n-1)p electrons are treated explicitly together with the ns electrons. By adding suitable correlating functions, we demonstrated that the present MCP basis sets show excellent performance in describing the electronic structures of atoms and molecules, bringing about accurate ionization potentials of atoms and very good spectroscopic constants of ionic and covalent molecules. The results obtained with the new MCPs are very close to the ones obtained using the all-electron correlation consistent basis sets of Dunning.     

Molecular depth-profiling of polycarbonate with low-energy Cs+ ions

In this work, we explored the possibility of performing molecular depth-profiling by using very low-energy (about 200 eV) monoatomic Cs(+) ions. We show, for the first time, that this simple approach is successful on polymer layers of polycarbonate (PC). Under 200 eV Cs(+) irradiation of PC, a fast decrease of all characteristic negatively charged molecular ion signals is first observed but, rather surprisingly, these signals reach a minimum before rising again. A steady state is reached at which time most specific PC fragments are detected, some with even higher signal intensity (e.g. C(6)H(5)O(-)) than before irradiation. It is believed that the implanted Cs plays a major role in enhancing the negative ionisation of molecular fragments, leading to their easy detection for all the profile, although some material degradation obviously occurs. In the positive ion mode, all molecular fragments of the polymer disappear very rapidly, but clusters combining two Cs atoms and one molecular fragment (e.g. Cs(2)C(6)H(5)O(+)) are detected during the profile, proving that some molecular identification remains possible. In conclusion, this work presents a simple approach to molecular depth-profiling, complementary to cluster ion beam sputtering.     

D abstraction by H at a D-saturated Ru(0 0 1) surface

D abstraction (ABS) by H at Ru(0 0 1) surfaces initially saturated with D adatoms has been investigated using in situ mass spectrometry. HD and D₂ desorption rates are measured at various surface temperatures T as a function of H exposure time. Yield of D₂ desorption increases with T, while that of HD is little affected. Analyzing the measured rate curves, HD and D₂ desorption orders are evaluated to be 1.7 ± 0.1 and 2.5 ± 0.1, respectively, with respect to D coverage θ_D. To pursue the origin of the derived non-integral reaction orders the rate curves are further analyzed with the rate equations constructed to involve several ABS channels. Consequently, we find that the HD desorption is mainly governed by a second-order rate law in θ_D rather than the conventional hot atom-mediated ABS reaction even when it is corrected to include an isotope effect on ABS. We argue that such second-order ABS kinetics becomes important when the H atoms in excited state of chemisorption have energetically relaxed to some extent, and thereby tend to reside at, e.g. hexagonal closed packed hollow sites, interacting with nearby adatoms. On the other hand, the D₂ rate curves can be fit with third-order kinetics, consistent with the Langmuir-Hinshelwood mechanism in a super-saturation state. The isotope effect plays an essential role in the ABS reaction of D abstraction by H which competes with H abstraction by H as D adatoms are replaced by H atoms.     

On strong unimodality of multivariate discrete distributions

A discrete function f defined on Zⁿ is said to be logconcave if for , , . A more restrictive notion is strong unimodality. Following Barndorff-Nielsen [O. Barndorff-Nielsen, Unimodality and exponential families, Commun. Statist. 1 (1973) 189-216] a discrete function is called strongly unimodal if there exists a convex function such that  if . In this paper sufficient conditions that ensure the strong unimodality of a multivariate discrete distribution, are given. Examples of strongly unimodal multivariate discrete distributions are presented.