Impedance spectroscopy and conductometric biosensing for probing catalase reaction with cyanide as ligand and inhibitor

In this work, a new biosensor was prepared through immobilization of bovine liver catalase in a photoreticulated poly (vinyl alcohol) membrane at the surface of a conductometric transducer. This biosensor was used to study the kinetics of catalase–H₂0₂ reaction and its inhibition by cyanide. Immobilized catalase exhibited a Michaelis–Menten behaviour at low H₂0₂ concentrations (< 100 mM) with apparent constant K_M^app = 84 ± 3 mM and maximal initial velocity V_M^app = 13.4 μS min^? 1. Inhibition by cyanide was found to be non-competitive and inhibition binding constant K_i was 13.9 ± 0.3 μM. The decrease of the biosensor response by increasing cyanide concentration was linear up to 50 μM, with a cyanide detection limit of 6 μM. In parallel, electrochemical characteristics of the catalase/PVA biomembrane and its interaction with cyanide were studied by cyclic voltammetry and impedance spectroscopy. Addition of the biomembrane onto the gold electrodes induced a significant increase of the interfacial polarization resistance R_P. On the contrary, cyanide binding resulted in a decrease of Rp proportional to KCN concentration in the 4 to 50 μM range. Inhibition coefficient I₅₀ calculated by this powerful label-free and substrate-free technique (24.3 μM) was in good agreement with that determined from the substrate-dependent conductometric biosensor (24.9 μM).     

Friedel-Craft acylation of ar-himachalene: synthesis of acyl-ar-himachalene and a new acyl-hydroperoxide

Friedel-Craft acylation at 100 °C of 2,5,9,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocycloheptene [ar-himachalene], a sesquiterpenic hydrocarbon obtained by catalytic dehydrogenation of α-, β- and γ-himachalenes, produces a mixture of two compounds: (3,5,5,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocyclohepten-2-yl)-ethanone (2, in 69% yield), with a conserved reactant backbone, and 3, with a different skeleton, in 21% yield. The crystal structure of 3 reveals it to be 1-(8-ethyl-8-hydroperoxy-3,5,5-trimethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-ethanone. In this compound O-H…O bonds form dimers. These hydrogen-bonds, in conjunction with weaker C-H…O interactions, form a more extended supramolecular arrangement in the crystal.     

Ni(0)-CMC-Na - nickel colloids in sodium carboxymethyl-cellulose: catalytic evaluation in hydrogenation reactions

A recyclable catalyst, Ni(0)-CMC-Na, composed of nickel colloids dispersed in a water soluble bioorganic polymer, sodium carboxymethylcellulose (CMC-Na), was synthesized by a simple procedure from readily available reagents. The catalyst thus obtained is stable and highly active in alkene hydrogenations.     

Sur les opérateurs de Dunford-Pettis positifs qui sont faiblement compacts

Nous donnons des conditions nécessaires et suffisantes pour que tout opérateur de Dunford-Pettis positif sur un treillis de Banach, soit faiblement compact et nous déduisons quelques conséquences.

     

Stabilization of unbounded bilinear control systems in Hilbert space

We consider bilinear control systems of the form y^′(t)=Ay(t)+u(t)By(t) where A generates a strongly continuous semigroup of contraction (etA)_t?0 on an infinite-dimensional Hilbert space Y whose scalar product is denoted by 〈.,.〉. We suppose that this system is unbounded in the sense that the linear operator B is unbounded from the state Y into itself. Tacking into account eventual control saturation, we study the problem of stabilization by (possibly nonquadratic) feedback of the form u(t)=−f(〈By(t),y(t)〉). Applications to the heat equation is considered.     

Efficient Synthesis of New 2H‐Chromene Retinoids Hybrid Derivatives by Suzuki Cross‐coupling Reactions

In an attempt to improve anticancer activity, a series of retinoids–chromene hybrids was described. The novel heterocyclic chromene–retinoids hybrid including oxygen as a heteroatom in a six‐membered cyclic ring (2H‐chromene or 2H‐1‐benzopyran) was designed and synthesized by introducing different groups such as an aromatic or styrylphenyl ring in 6‐position of 2H‐chromene. These novel compounds were synthesized by using the efficient cascades one‐pot process involving Wittig–Horner–Emmons reaction and Suzuki–Miyaura cross‐coupling pallado‐catalyzed reactions with 60% to 90% overall yields. These new compounds were tested against glioblastoma multiforme brain cancer, medulloblastoma, neuroblastoma cell lines, and breast cancer MCF‐7 cell lines. Two of them exhibited an appreciable anti‐tumor activity in the low micromolar range, which opens new perspectives for therapeutic application on humans.     

Novel palladium nanoparticles supported on mesoporous natural phosphate: Catalytic ability for the preparation of aromatic hydrocarbons from natural terpenes

Various ratios of palladium nanoparticles supported on mesoporous natural phosphate (Pd@NP) were prepared using the wetness impregnation method. The prepared catalysts were characterized by IR, XRD, CV, SEM, EDX, XRF, TEM and BET analysis. The reduction and preparation of the palladium nanoparticles afford a crystallite size of 10.88 nm. The performance of the synthesized catalyst was investigated in the solvent-free dehydroaromatization of α-, β- and γ-himachalene mixture from Cedrus atlantica oil as a model substrate. In order to achieve an efficient and selective catalysis, the catalytic dehydroaromatization of various terpenes such as limonene, limonaketone, carvone, carveol and perillyl alcohol was studied. The Pd@NP catalyst performed a high catalytic activity, selectivity and recyclability in the terpenes dehydroaromatization reaction.     

Trace element content of medicinal plants from Algeria

Neutron activation analysis (INAA) has been applied to multielemental determination of eleven medicinal plants used to cure the urinary tract diseases observed in Algeria. These plants include Androgena Citratus, Ceratonia Siliquata, Punica Granatum, Glyryrrhiza Glabra, Lausaunia Alba, Fragaria Vesca, Arbutus Unedol, Hordeum Vulgaris, Papieteria Officinalis, Zea Mays L, and Davallia Seae. Concentrations of twenty elements Ba, Br, Ca, Cl, Co, Cu, Cr, Fe, I, Mn, Na, Mg, Rb, Sb, Se, Sc, Sr, Ti, V, and Zn have been determined by short, and long irradiation times with a thermal and epithermal flux of 1.4·10¹² n·cm⁻²·s⁻¹ and 1.4·10¹¹ n·cm⁻²·s⁻¹, respectively. These analyses were performed in conjunction with Compton suppression. In almost herbs studied the Co, Cr, Cu, Rb, Sb, Sc, Se and V are found to be present at trace levels, Br, Mn, and Zn at the minor level, and Ca, Cl, Fe, Mg and Na are generally at the major level. The accuracy of the measurements has been evaluated by analyzing NIST-botanical references materials.     

Finite element reduced order model for noise and vibration reduction of double sandwich panels using shunted piezoelectric patches

This work concerns the control of sound transmission through double laminated panels with viscoelastic core using semi-passive piezoelectric shunt technique. More specifically, the system consists of two laminated walls, each one composed of three layers and called sandwich panel with an air cavity in between. The external sandwich panel has a surface-mounted piezoelectric patches. The piezoelectric elements, connected with resonant shunt circuits, are used for the vibration damping of some specific resonance frequencies of the coupled system. Firstly, a finite element formulation of the fully coupled visco-electro-mechanical-acoustic system is presented. This formulation takes into account the frequency dependence of the viscoelastic material. A modal reduction approach is then proposed to solve the problem at a lower cost. In the proposed technique, the coupled system is solved by projecting the mechanical displacement unknown on a truncated basis composed by the first real short-circuit structural normal modes and the pressure unknown on a truncated basis composed by the first acoustic modes with rigid boundaries conditions. The few initial electrical unknowns are kept in the reduced system. A static correction is also introduced in order to take into account the effect of higher modes. Various results are presented in order to validate and illustrate the efficiency of the proposed finite element reduced order formulation.     

Are Unsaturated Isocyanides so Different from the Corresponding Nitriles?

Simple unsaturated and cyclopropylic isocyanides are synthesized by an efficient and simple approach. These compounds with gradually increasing distance between the unsaturated moiety and the isonitrile group are studied by UV photoelectron spectroscopy and quantum chemical calculations, and also compared to the corresponding nitriles. The first photoelectron band of the unsaturated compounds is linked to removal of an electron from the HOMO, which corresponds to CC multiple-bond ionization in antibonding interaction with the π-isocyanide bond (in the same plane) for conjugated systems, or in antibonding interaction with the pseudo-π-CH(2) group for isolated systems. For the 1-ethenyl derivatives, both cyano and isocyano groups act as a π-electron acceptor from the vinyl group, but the isocyano π system is much more strongly destabilized (ionization energies (IEs) shift to smaller values) by vinyl (3.12 eV) than the cyano π system is (2.70 eV). In comparison with the 1-ethynyl derivatives, a less pronounced destabilization (2.69 eV) of π(NC) by the ethynyl system (1.86 eV for π(CN)), and nearly the same order of magnitude of the energetic gap between the total antibonding (π(CC)-π(NC)) and the total bonding (π(CC)+π(NC)) IEs for ethenyl and ethynyl compounds are noted. The huge values of these last-named data for H(2)C=CH-NC (3.85 eV) and for HC≡C-NC (4.04 eV) reflect the strong interaction between the unsaturated carbon-carbon moiety and the isocyanide group, and thus more efficient conjugation than for the corresponding nitriles.