MIP‐esterase/Tyrosinase Combinations for Paracetamol and Phenacetin

A new electrochemical MIP sensor for the most frequently used drug paracetamol (PAR) was prepared by electropolymerization of mixtures containing the template molecule and the functional monomers o‐phenylenediamine, resorcinol and aniline. The imprinting factor of 12 reflects the effective target binding to the MIP as compared with the non‐imprinted electropolymer. Combination of the MIP with a nonspecific esterase allows the measurement of phenacetin – another analgesic drug. In the second approach the PAR containing sample solution was pretreated with tyrosinase in order to prevent electrochemical interferences by ascorbic acid and uric acid. Interference‐free indication at a very low electrode potential without fouling of the electrode surface was achieved with the o‐phenylenediamine: resorcinol‐based MIP.     

Insights into the Ultrafast Photodissociation Dynamics of Isoprene-Derived Criegee Intermediates

Isoprene is the most abundant nonmethane volatile organic compound emitted into the troposphere by terrestrial vegetation. Reaction with ozone represents an important isoprene removal process from the troposphere and is a well-known source of Criegee intermediates (CIs), which are reactive carbonyl oxides. Three CIs, formaldehyde oxide (CH₂OO), methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide) are formed during isoprene ozonolysis. All three CIs contain strongly absorbing ππ* states, electronic excitation, which leads to dissociation to form aldehyde/ketone + oxygen products. Here, we compare the excited state chemistry of CH₂OO, MVK-oxide and MACR-oxide in order to ascertain how increasing molecular complexity affects their photodynamics. In CH₂OO, vertical excitation to the S₂ state leads to prompt O-O bond fission with a unity quantum yield. Branching into both the O (¹D) + H₂CO (S₀) and O (³P) + H₂CO (T₁) product channels is predicted, with 80% of trajectories dissociating to form the former product pair. Analogous vertical excitation of the lowest energy conformers of MVK-oxide and MACR-oxide also undergoes O-O bond fission to form O + MVK/MACR products—albeit with a nonunity quantum yield. In the latter case, ca. 10% and 25% of trajectories remain as the parent MVK-oxide and MACR-oxide molecules, respectively. Additionally, at most only 5% of the dissociating trajectories form O (³P) + MVK/MACR (T₁) products, with a greater fraction forming O (¹D) + MVK/MACR (S₀) products (cf. CH₂OO). This latter observation coupled with the greater fraction of undissociated trajectories aligns with the bathochromic shift in the electronic absorption of the MACR-oxide and MVK-oxide (cf. CH₂OO). We discuss the implications of the results in a broader context, including those that are relevant to the atmosphere.     

Synthesis, spectral and thermal properties, and crystal structure of catena-poly-μ-ethylenediamine(dipicolinato)zinc(II) trihydrate, {[Zn(dipic)(μ-en)]·3H2O}n

A novel metal–organic coordination polymer framework formulated as {[Zn(dipic)(μ-en)]·3H₂O} _n (1) (catena-poly-μ-ethylenediamine(dipicolinato)zinc(II) trihydrate) has been synthesized and characterized by spectral method (IR), elemental analysis, thermal analysis (TG, DTG, DTA) and single crystal X-ray diffraction techniques. It crystallizes in the triclinic system, space group P−1. The asymmetric unit contains three hydrogen-bonded water molecules and the Zn atom is five-coordinated by three N and two O atoms. In fact, it is a new one-dimensional zinc complex with the peculiarity of having the ethylenediamine ligand very unusually acting as bridge to form polymeric chains. In the crystal structure, intramolecular O–H···O and intermolecular O–H···O and N–H···O hydrogen bonds result in the formation of a supramolecular structure, in which they seem to be effective in the stabilization of the structure.     

Phase boundary propagation in large LiFePO4 single crystals on delithiation

Large single crystals of LiFePO(4) have been chemically delithiated. The relevance of chemical oxidation in comparison with electrochemical delithiation is discussed. Analyses of the Li content and profiles were done by electron energy loss spectroscopy and secondary ion mass spectrometry. The propagation of the FePO(4) phase growing on the surface of the large single crystal was followed by in situ optical microscopy as a function of time. The kinetics were evaluated in terms of linear irreversible thermodynamics and found to be characterized by an induction period followed by parabolic growth behavior of the FePO(4) phase indicating transport control. The growth rate was shown to depend on the crystallographic orientation. Scanning electron microscopy images showed cracks and a high porosity of the FePO(4) layer due to the significant changes in the molar volumes. The transport was found to be greatly enhanced by the porosity and crack formation and hence greatly enhanced over pure bulk transport, a result which is supposed to be very relevant for battery research if coarse-grained powder is used.     

Electroanalytical Studies and Simultaneous Determination of Amlodipine Besylate and Atorvastatine Calcium in Binary Mixtures Using First Derivative of the Ratio‐Voltammetric Methods

The electrochemical behavior of atorvastatin and amlodipine at a glassy carbon electrode has been studied using different voltammetric techniques. First derivative of the ratio voltammetric methods for determination of amlodipine and atorvastatin in tablets in the presence of the other compound has been described. This technique depends on the measuring of first derivative of the ratio voltammograms of each concentration as a function of the increased concentrations. DP and SW voltammetric methods depend on first derivative of the ratio‐voltammetry by measurements of the selected potentials for amlodipine and atorvastatin. The linear response was within the range of 4×10^?6–1×10^?4 M for amlodipine and 2×10^?6–1×10^?4 M for atorvastatin. The proposed methods have been extensively validated.     

Edge-enhanced spatiotemporal constrained reconstruction of undersampled dynamic contrast-enhanced radial MRI

Dynamic contrast-enhanced magnetic resonance imaging (MRI) is a technique used to study and track contrast kinetics in an area of interest in the body over time. Reconstruction of images with high contrast and sharp edges from undersampled data is a challenge. While good results have been reported using a radial acquisition and a spatiotemporal constrained reconstruction (STCR) method, we propose improvements from using spatially adaptive weighting and an additional edge-based constraint. The new method uses intensity gradients from a sliding window reference image to improve the sharpness of edges in the reconstructed image. The method was tested on eight radial cardiac perfusion data sets with 24 rays and compared to the STCR method. The reconstructions showed that the new method, termed edge-enhanced spatiotemporal constrained reconstruction, was able to reconstruct images with sharper edges, and there were a 36%±13.7% increase in contrast-to-noise ratio and a 24%±11% increase in contrast near the edges when compared to STCR. The novelty of this paper is the combination of spatially adaptive weighting for spatial total variation (TV) constraint along with a gradient matching term to improve the sharpness of edges. The edge map from a reference image allows the reconstruction to trade-off between TV and edge enhancement, depending on the spatially varying weighting provided by the edge map.     

Integrated cellular manufacturing systems design with production planning and dynamic system reconfiguration

This paper presents and analyzes a comprehensive model for the design of cellular manufacturing systems (CMS). A recurring theme in research is a piecemeal approach when formulating CMS models. In this paper, the proposed model, to the best of the authors’ knowledge, is the most comprehensive one to date with a more integrated approach to CMS design, where production planning and system reconfiguration decisions are incorporated. Such a CMS model has not been proposed before and it features the presence of alternate process routings, operation sequence, duplicate machines, machine capacity and lot splitting. The developed model is a mixed integer non-linear program. Linearization procedures are proposed to convert it into a linearized mixed integer programming formulation. Computational results are presented by solving some numerical examples, extracted from the existing literature, with the linearized formulation.     

A Lagrangean relaxation and decomposition algorithm for the video placement and routing problem

Video on demand (VoD) is a technology used to provide a number of programs to a number of users on request. In developing a VoD system, a fundamental problem is load balancing, which is further characterized by optimally placing videos to a number of predefined servers and routing the user program requests to available resources. In this paper, an exact solution algorithm is described to solve the video placement and routing problem. The algorithm is based on Lagrangean relaxation and decomposition. The novelty of the approach can be described as the use of integer programs to obtain feasible solutions in the algorithm. Computational experimentation reveals that for randomly generated problems with up to 100 nodes and 250 videos, the use of such integer programs help greatly in obtaining good quality solutions (typically within 5% of the optimal solution), even in the very early iterations of the algorithm.     

Electrochemical polymerisation of 2-aminofluorene in ethylalcohol/water medium

Electrochemical polymerisation of 2-aminofluorene, 2AF, was investigated in ethylalcohol/water mixture (3:2, v:v) in the presence of HClO₄ as the supporting electrolyte via constant potential electrolysis, CPE. Prior to CPE, electrochemical behaviour of the monomer was investigated in the same solvent-electrolyte couple utilising cyclic voltammetry, CV. Electrochemical polymerisation of the monomer yielded insoluble, dark bluish-green, conducting polymer deposit on the electrode surface. Characterisation of the polymer film has been carried out using FT-IR spectroscopic technique and thermal behaviour was studied using differential scanning calorimetry, DSC. Spectroelectrochemical, SPEL, behaviour of the polymer on ITO working electrode was studied by recording the electronic absorption spectra, in situ, in monomer-free solution at different potentials and it is found that the film can be reversibly cycled between −0.1 and 1.1 V vs SCE. Paramagnetic behaviour of the polymer was monitored using in situ ESR spectroscopy. The temperature dependence of conductivity supported the Mott's variable range hopping, VRH, mechanism for poly(aminofluorene), PAF.