Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes.     

Lot Streaming in a Two-stage Flow Shop with Set-up,Processing and Removal Times Separated

This paper considers the job (lot) scheduling problem for two-stage flow shops in which the movement of transfer batches (sublots) from the first stage to the next are allowed. Set-up, processing and removal times are considered as separable and independent of the order in which jobs are processed at any of two stages. An optimal transfer batch sizing and scheduling algorithm which has an objective of minimizing the maximum flow time (makespan) is developed and demonstrated by a numerical example.     

Modification of the cation exchange resin properties by impregnation in polyethyleneimine solutions: application to the separation of metallic ions

A commercial cation exchange resin Amberlite 200 has been modified after immersion in solutions of polyethyleneimine (PEI). The kinetic of fixation of the metallic ions have been determined. The modification of the surface of the resin deals with a change in the order of the affinities of the resins towards cations. The retention is the function of the formation and the stability of the complex. The conditions of modification (pH, PEI concentration and time of immersion) have been examined and the modification was confirmed by the determination of the exchange capacities, the distribution coefficient (P) and the selectivity factors (S). The obtained results revealed the effect of PEI on the exchange properties of the resin. The pH range selected (6-8) permitted a good adherence of PEI onto the resin surface. The quantity of the adsorbed PEI was increased by raising the initial concentration and the immersion period. The exchange capacity for copper ion passed from 2.6 mmol g⁻¹, in the case of unmodified resin, to 3.9 mmol g⁻¹ for the modified one.     

Natural Melanin Nanoparticle‐decorated Screen‐printed Carbon Electrode: Performance Test for Amperometric Determination of Hexavalent Chromium as Model Trace

A biosensor was prepared with natural melanin nanoparticles (MNP) decorated on a screen‐printed carbon electrode (SPCE). Hexavalent chromium was selected as a well‐known heavy metal ion to be detected for testing the performance of novel biosensor. Natural MNP was extracted from cuttlefish (Sepia officinalis) ink. Surface decoration of SPCEs with MNP was performed by two different methods. The first one was layer‐by‐layer assembly (LBL‐A) for different cycle times(n). In the second one, plasma treatment of SPCE incorporated with evaporation‐induced self‐assembly (EI‐SA) techniques including different incubation times in MNP solutions. The performance of both modified SPCEs were tested for amperometric detection of Cr(VI) in various water samples, and peak reduction of Cr(VI) was determined at 0.33 V. Amperometric results showed wide linear ranges of 0.1–2 μM and 0.1–5 μM of Cr(VI) for SPCEs modified with 14n‐LBL‐A and 12h‐EI‐SA, respectively. The sensitivities of SPCEs modified with 14n‐LBL‐A and 12h‐EI‐SA techniques were 0.27 μA μM^?1 and 0.52 μA μM^?1, respectively. In addition, both modified SPCEs selectively detected Cr(VI) in a model aqueous system composed of certain other heavy metals and minerals, and tap and lake water samples. The LOD and LOQ values for 12h‐EI‐SA were 0.03 μM and 0.1 μM, respectively. This showed that MNP‐modified‐SPCEs generated via EI‐SA techniques have the potential to be an alternative to conventional detection methods such as ICP‐MS.     

Wavelet packet based analysis of sound fields in rooms using coincident microphone arrays

This paper presents a passive analysis method for determining the spatio-temporal characteristics of sound fields in small rooms. The analysis finds an approximate directional reflectogram (ADR) which reveals the approximate arrival directions, time delays and amplitudes of the direct sound and early reflections without using a special or known sound source. A coincident microphone array is used to obtain directional recordings. The recordings are analysed by wavelet packet decomposition to determine the direction of the sound source and select wavelet packet coefficients to reconstruct the estimate of the direct sound. ADR is then computed via deconvolution using this estimate. Experiments have been carried out using synthesized recordings that were obtained from actual room impulse responses measured in two rooms for various source locations. The method estimates the source direction with a mean absolute error of about 7°. Calculated ADRs provide a good estimate of the time delays and arrival directions of acoustical reflections, whereas the amplitudes differ slightly.     

Synthesis,structural, spectral,thermal and comparative biological activity studies of [V<Subscript>2</Subscript>O<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>]

The hydrothermal reaction of a mixture of V₂O₅, VCl₃, 2,5-pyridinedicarboxylic acid and diluted H₂SO₄ for 68 h at 180°C gives a blue colored solution which yields prismatic blue crystals of IV ₂ ^IV O₂(SO₄)₂(H₂O)₆] (1) in 32% yield (based on V). Complex 1 was investigated by means of elemental analysis (C, H and S), TGA, FT-IR, manganometric titration, Single Crystal X-ray Diffraction Methods and also comparative antimicrobial activities. Crystal data for the compound: monoclinic space group P2₁/c and unit cell parameters are a = 7.3850(12) Å, b = 7.3990(7) Å, c = 12.229(2) Å, β = 108.976(12)° and Z = 2. Although structure of 1 as a natural mineral has been previously determined, this work covers new preparation method and full characterization of 1 along with comparison of antibacterial activity between 1 and the commercial vanadium(IV) oxide sulfate hydrate compounds, VOSO₄ · xH₂O (Riedel-de Haën and Alfa Aesar brand names). 1 was evaluated for the antimicrobial activity against gram-positive, gram-negative bacteria, yeasts and mould compared with the commercial VOSO₄ · xH₂O compounds. 1 showed weak activity against bacteria Bacillus cereus, Nocardia asteroides and yeast Candida albicans. A good antimicrobial activity was recorded against Cirtobacter freundii (15 mm). There are only a few reproducible well-defined vanadium(IV) starting materials to use for exploring the synthesis of new materials. VCl₄, VO(acac)₂, VOSO₄ · xH₂O and [V(IV)OSO₄(H₂O)₄] · SO₄ · [H₂N(C₂H₄)₂NH₂] are common starting materials for such applications. In addition to these compounds, 1 can be used as an oxovanadium precursor.     

Study of various parameters influencing the fixation of metallic ions Cu2+, Zn2+, and Ni2+ at the catalytic Amberlyst-15 resin in the presence of alcohols

The ionic exchange behavior of Zn²⁺, Ni²⁺, and Cu²⁺ metallic ions on Amberlyst-15 commercial resin was studied as a function of resin solution contact time, initial concentration of metallic ions, nature of the solvent, and the amount of resin. The metallic ions were studied in ternary mixtures using both column and batch experiments. In addition, water, methanol, ethanol, and propan-2-ol were used as solvents for dissolving metallic ions. It was found that the resin behavior depends on the solvent nature and the metallic ion concentration. The analysis of solutions by atomic absorption spectrometry revealed that the affinity of the resin for the studied metallic ions followed the sequence Cu²⁺ > Ni²⁺ > Zn²⁺ in the case of an aqueous medium. Furthermore, uptake increased with increasing amount of resin. A better uptake was observed in the case of the 75:25 % water/methanol compositions when the column technique was used. For the batch technique, we noted a better uptake using 100 % water. The uptake rate decreased with an increase in the number of carbons for the 50 % water–50 % alcohol solvents. The acid–base properties of Amberlyst-15 commercial resin were studied by 2-propanol decomposition test. Propene and acetone are the main expected products and it is believed that they are formed through dehydration or dehydrogenation reaction on acid and base sites, respectively.     

Large Deviations of the Threshold Estimator of Integrated (Co-)Volatility Vector in the Presence of Jumps

Recently considerable interest has been paid to the estimation problem of the realized volatility and covolatility by using high-frequency data of financial price processes in financial econometrics. Threshold estimation is one of the useful techniques in the inference for jump-type stochastic processes from discrete observations. In this paper, we adopt the threshold estimator introduced by Mancini (Scand Actuar J 1:42–52, 2004) where only the variations under a given threshold function are taken into account. The purpose of this work is to investigate large and moderate deviations for the threshold estimator of the integrated variance–covariance vector. This paper is an extension of the previous work in Djellout et al. (Stoch Process Appl 1–35, 2017), where the problem has been studied in the absence of a jump component. We will use the approximation lemma to prove large and moderate deviations results. As the reader can expect, we obtain the same results as in the case without jump.     

Moderate deviations for martingale differences and applications to φ -mixing sequences

For a R d -valued sequence of martingale differences { m k } k S 1 , we obtain a moderate deviation principle for the sequence of partial sums { Z n ( t ) 1 ~ k =1 [ nt ] m k / b n , t ] [0,1]}, in the space of càdlàg functions equipped with the Skorohod topology, under the following conditions: a Chen-Ledoux type condition, an exponential convergence in probability of the associated quadratic variation process of the martingale, and a condition of "Lindeberg" type. For the small jumps of Z n (·), we apply the general result of Puhalskii [Puhalskii, A. (1994). "Large deviations of semimartingales via convergence of the predictable characteristics". Stoch. Stoch. Rep. , 49 , pp. 27-85]. Following the method of Ledoux [Ledoux, M. (1992). "Sur les déviations modérées des sommes de variables aléatoires vectorielles indépendantes de même loi". Ann. Inst. H. Poincaré , 28 , pp. 267-280] and Arcones [Arcones, A. (1999). "The large deviation principle for stochastic processes", Submitted for publication], we prove that the large jumps part of Z n (·) is negligible in the sense of the moderate deviations. One can regard our result as an extension to martingale differences, of the beautiful characterization of moderate deviations for i.i.d.r.v. case due to Chen [Chen, X. (1991). "The moderate deviations of independent vectors in Banach space". Chin. J. Appl. Probab. Stat. , 7 , pp. 124-32] and Ledoux [Ledoux, M. (1992). "Sur les déviations modérées des sommes de variables aléatoires vectorielles indépendantes de même loi". Ann. Inst. H. Poincaré , 28 , pp. 267-280]. Using the Gordin [Gordin, M.I. (1969). "The central limit theorem for stationary processes". Soviet Math. Dokl. , 10 , pp. 1174-1176] decomposition, the martingale result is applied to prove the moderate deviation principle for a wide class of stationary { -mixing sequences of random variables.