Extended viologen as a source of electric oscillations

A long organic molecule 1 with five bipyridinium functions separated by benzene rings (extended viologen) undergoes a reversible multi-step electron transfer. Here we show that this decacation accepts electrons at the heterogeneous interface with the occurrence of the periodically changing electric reduction currents. According to the applied bias voltage the observed current-time dependence changes from chaotic through periodic and irregular to sinusoidal and finally to monotonous. A careful choice of the controlling parameters yields the sustained periodic sinusoidal currents lasting for a prolonged time. Oscillations stem from a mutual interplay of the heterogeneous supply of electrons and the homogeneous redox reactions (disproportionation) between the transient redox forms. In difference to many other electrochemical oscillating systems the described oscillations do not require any additional external impedance. The principle of these oscillatory currents may serve as a model of a truly 'molecular oscillator'.     

High sensitive matrix-free mass spectrometry analysis of peptides using silicon nanowires-based digital microfluidic device

We present for the first time an electrowetting on dielectric (EWOD) microfluidic system coupled to a surface-assisted laser desorption-ionization (SALDI) silicon nanowire-based interface for mass spectrometry (MS) analysis of small biomolecules. Here, the transfer of analytes has been achieved on specific locations on the SALDI interface followed by their subsequent mass spectrometry analysis without the use of an organic matrix. To achieve this purpose, a device comprising a digital microfluidic system and a patterned superhydrophobic/superhydrophilic silicon nanowire interface was developed. The digital microfluidic system serves for the displacement of the droplets containing analytes, via an electrowetting actuation, inside the superhydrophilic patterns. The nanostructured silicon interface acts as an inorganic target for matrix-free laser desorption-ionization mass spectrometry analysis of the dried analytes. The proposed device can be easily used to realize several basic operations of a Lab-on-Chip such as analyte displacement and rinsing prior to MS analysis. We have demonstrated that the analysis of low molecular weight compounds (700 m/z) can be achieved with a very high sensitivity (down to 10 fmol μL(-1)).     

The comparison of sample extraction procedures for the determination of cations in soil by IC and ICP-AES

This paper presents the extraction of cations from a soil sample, type ranker on serpentinite, in deionized water, by use of three different extraction techniques. The first extraction technique included the use of a rotary mixer, the second technique involved the use of a microwave digestion system with different extraction temperatures, and the third technique employed an ultrasonic bath with different extraction times. Ion chromatography was used for determining the concentration of Li, Na, K, Ca, Mg and ammonium ions in soil extracts with subsequent determination of concentrations for all cations, except for ammonium ion extraction, conducted by Inductively Coupled Plasma-Atomic Emission Spectrometry. The results of cation extractions showed that microwave assisted extraction was most efficient for the Li, Na, K, Ca, Mg, Co, Mn, Ni, Pb and ammonium ions. Use of a rotary mixer for extraction was most efficient for Cd and Zn ions, while use of ultrasound bath was most efficient for Cr, Cu, Fe and Al ions. Several times higher amount of cations extracted by the most efficient, compared to the second best technique, under optimal conditions, were noticed in the case of: Ca, Mg, Co, Mn, Fe, Al, and Zn ions.     

Major elements as possible factors of trace element urban pedochemical anomalies

The relationship between real total contents of the major elements Na, Mg, Al, Si, P, S, K, Ca, Ti, Fe and the trace elements Ag, As, B, Ba, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Sn, V, U, Zn in topsoil from the central part of Vilnius is analysed. The amounts of most elements were determined by energy-dispersive X-ray fluorescence, while amounts of Ag, B, Co were measured by optical atomic emission spectrophotometry. Two factors were distinguished according to major elements: anthropogenic (A) including Ca, Mg, Fe, P, S and clayey (C) including K, Al, Ti. Boron, Mn, Cr and U are significantly correlated with members of both factors, Sb with none of them and other trace elements either with all (Cu, Zn, Pb, Se, Ba, Ni, Co) or with separate (V, Ag, Sn, Mo, As) members of the A-factor. Only B, Mn, Cr, U (partly their additive index Z1) are influenced by the C-factor, while twelve other trace elements (also their additive index Z2) are influenced by the A-factor. The additive index Z of all 17 elements is also affected by the A-factor. Four groups of sites have been distinguished according to normal or higher contents of both factors. The majority of trace element anomalies are related to the sites affected by the A-factor.     

Variability of essential oils of Betonica officinalis (Lamiaceae) from different wild populations in Kosovo

The aerial parts and roots of Betonica officinalis were collected from three localities characterized by different ecological conditions to study the natural variability of the chemical composition of the essential oils in this plant. The leaves and inflorescences were collected during the flowering time, whereas the roots were collected at the end of the vegetative period. The plant material was dried at room temperature. The essential oils were obtained by micro-steam hydrodistillation and analyzed using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Overall, 69 constituents were identified in all localities and plant parts. The main compositions of the leaves in all localities were alpha-pinene, 1-octen-3-ol, beta-bourbonene, (E)-caryophyllene and germacrene D. The essential oil of the inflorescences was characterized by these main constituents: alpha-pinene, (E)-caryophyllene and trans-beta-farnesene. In all localities, the percentages of alpha-pinene and (E)-caryophyllene were higher in the inflorescences than in the leaves, whereas nonane was the main constituent in the roots.     

Dynamic fracture of concrete – compact tension specimen

The behavior of concrete structures is strongly influenced by the loading rate. Compared to quasi-static loading concrete loaded by impact loading acts in a different way. First, there is a strain-rate influence on strength, stiffness, and ductility, and, second, there are inertia forces activated. Both influences are clearly demonstrated in experiments. Moreover, for concrete structures, which exhibit damage and fracture phenomena, the failure mode and cracking pattern depend on loading rate. In general, there is a tendency that with the increase of loading rate the failure mode changes from mode-I to mixed mode. Furthermore, theoretical and experimental investigations indicate that after the crack reaches critical speed of propagation there is crack branching. The present paper focuses on 3D finite-element study of the crack propagation of the concrete compact tension specimen. The rate sensitive microplane model is used as a constitutive law for concrete. The strain-rate influence is captured by the activation energy theory. Inertia forces are implicitly accounted for through dynamic finite element analysis. The results of the study show that the fracture of the specimen strongly depends on the loading rate. For relatively low loading rates there is a single crack due to the mode-I fracture. However, with the increase of loading rate crack branching is observed. Up to certain threshold (critical) loading rate the maximal crack velocity increases with increase of loading rate, however, for higher loading rates maximal velocity of the crack propagation becomes independent of the loading rate. The critical crack velocity at the onset of crack branching is found to be approximately 500 m/s.     

Refractive-index and density matching in concentrated particle suspensions: a review

Optical measurement techniques such as particle image velocimetry (PIV) and laser Doppler velocimetry (LDV) are now routinely used in experimental fluid mechanics to investigate pure fluids or dilute suspensions. For highly concentrated particle suspensions, material turbidity has long been a substantial impediment to these techniques, which explains why they have been scarcely used so far. A renewed interest has emerged with the development of specific methods combining the use of iso-index suspensions and imaging techniques. This review paper gives a broad overview of recent advances in visualization techniques suited to concentrated particle suspensions. In particular, we show how classic methods such as PIV, LDV, particle tracking velocimetry, and laser induced fluorescence can be adapted to deal with concentrated particle suspensions.     

Two-sided bounds for the volume of right-angled hyperbolic polyhedra

For a compact right-angled polyhedron R in Lobachevskii space ?³, let vol(R) denote its volume and vert(R), the number of its vertices. Upper and lower bounds for vol(R) were recently obtained by Atkinson in terms of vert(R). In constructing a two-parameter family of polyhedra, we show that the asymptotic upper bound 5v ₃/8, where v ₃ is the volume of the ideal regular tetrahedron in ?³, is a double limit point for the ratios vol(R)/ vert(R). Moreover, we improve the lower bound in the case vert(R) ≤ 56.     

The curse of dimensionality for the class of monotone functions and for the class of convex functions

We study the integration and approximation problems for monotone or convex bounded functions that depend on $d$ variables, where $d$ can be arbitrarily large. We consider the worst case error for algorithms that use finitely many function values. We prove that these problems suffer from the curse of dimensionality. That is, one needs exponentially many (in $d$) function values to achieve an error $\epsilon$.     

New higher-order methods for the simultaneous inclusion of polynomial zeros

Higher-order methods for the simultaneous inclusion of complex zeros of algebraic polynomials are presented in parallel (total-step) and serial (single-step) versions. If the multiplicities of each zeros are given in advance, the proposed methods can be extended for multiple zeros using appropriate corrections. These methods are constructed on the basis of the zero-relation of Gargantini’s type, the inclusion isotonicity property and suitable corrections that appear in two-point methods of the fourth order for solving nonlinear equations. It is proved that the order of convergence of the proposed methods is at least six. The computational efficiency of the new methods is very high since the acceleration of convergence order from 3 (basic methods) to 6 (new methods) is attained using only n polynomial evaluations per iteration. Computational efficiency of the considered methods is studied in detail and two numerical examples are given to demonstrate the convergence behavior of the proposed methods.