New group 11 complexes with metal-selenium bonds of methyldiphenylphosphane selenide: a solid state, solution and theoretical investigation

Reactions between methyldiphenylphosphane selenide, SePPh(2)Me, and different group 11 metal starting materials {CuCl, [CuNO(3)(PPh(3))(2)], AgOTf, [AgOTf(PPh(3))] (OTf = OSO(2)CF(3)), [AuCl(tht)], [Au(C(6)F(5))(tht)] and [Au(C(6)F(5))(3)(tht)] (tht = tetrahydrothiophene)} were performed in order to obtain several new species with metal-selenium bonds. The new complexes [CuCl(SePPh(2)Me)] (1), [AgOTf(SePPh(2)Me)] (2), [AuCl(SePPh(2)Me)] (5), [Au(C(6)F(5))(SePPh(2)Me)] (6) and [Au(C(6)F(5))(3)(SePPh(2)Me)] (7) were isolated and structurally characterized in solution by multinuclear NMR spectroscopy ((1)H, (31)P, (77)Se and (19)F where appropriate). Solid products were isolated also from the reactions between SePPh(2)Me and [CuNO(3)(PPh(3))(2)] or [AgOTf(PPh(3))], respectively. NMR experiments, including low temperature (1)H and (31)P NMR, revealed for them a dynamic behaviour in solution, involving the transfer of selenium from PPh(2)Me to PPh(3). In case of the isolated silver(i) containing solid an equilibrium between, respectively, monomeric [AgOTf(PPh(3))(SePPh(2)Me)] (3) and [AgOTf(PPh(2)Me)(SePPh(3))] (4), and dimeric [Ag(PPh(3))(μ-SePPh(2)Me)](2)(OTf)(2) (3a) and [Ag(PPh(2)Me)(μ-SePPh(3))](2)(OTf)(2) (4a) species was observed in solution. In case of the isolated copper(i) containing solid the NMR studies brought no clear evidence for a similar behaviour, but it can not be excluded in a first stage of the reaction. However the transfer of selenium between the two triorganophosphanes takes place also in this case, but the NMR spectra suggest that the final reaction mixture contains the free triorganophospane selenides SePPh(2)Me and SePPh(3) as well as the complex species [CuNO(3)(PPh(3))(2)], [CuNO(3)(PPh(2)Me)(2)] and [CuNO(3)(PPh(3))(PPh(2)Me)] in equilibrium. Single-crystal X-ray diffraction studies revealed monomeric structures for the gold(I) 6 and gold(III) 7 complexes. In case of compound 6 weak aurophilic gold(I)···gold(I) contacts were also observed in the crystal. DFT calculations were performed in order to understand the solution behaviour of the silver(I) and copper(I) species containing both P(III) and P(V) ligands, to verify the stability of possible dimeric species and to account for the aurophilic interactions found for 6. In addition, the nature of the electronic transitions involved in the absorption/emission processes observed for 6 and 7 in the solid state were also investigated by means of TD-DFT calculations.     

Cleft Comodule Categories

We define crossed product categories and we show that they are equivalent with cleft comodule categories. We also prove that a comodule category is cleft if and only if it is Hopf–Galois and has a normal basis. As an application we show that the category of Hopf modules over a cleft linear category and the category of modules over the coinvariant subcategory are equivalent.     

Optimal control of a signorini contact problem

We are interested in finding the coefficient of friction which leads us to a given displacement on the contact surface between an elastic solid body and a rigid foundation. The mathematical formulation of the problem is an optimal control problem governed by a quasivariational inequality. We obtain an approximative caracterization, by using two families of penalized and regularized problems, for a given optimal control.     

Potent antimicrobial small molecules screened as inhibitors of tyrosine recombinases and Holliday junction-resolving enzymes

Holliday junctions (HJs) are critical intermediates in many recombination-dependent DNA repair pathways. Our lab has previously identified several hexameric peptides that target HJ intermediates formed in DNA recombination reactions. One of the most potent peptides, WRWYCR, is active as a homodimer and has shown bactericidal activity partly because of its ability to interfere with DNA repair proteins that act upon HJs. To increase the possibility of developing a therapeutic targeting DNA repair, we searched for small molecule inhibitors that were functional surrogates of the peptides. Initial screens of heterocyclic small molecule libraries resulted in the identification of several N-methyl aminocyclic thiourea inhibitors. Like the peptides, these inhibitors trapped HJs formed during recombination reactions in vitro, but were less potent than the peptides in biochemical assays and had little antibacterial activity. In this study, we describe the screening of a second set of libraries containing somewhat larger and more symmetrical scaffolds in an effort to mimic the symmetry of a WRWYCR homodimer and its target. From this screen, we identified several pyrrolidine bis-cyclic guanidine inhibitors that also interfere with processing of HJs in vitro and are potent inhibitors of Gram-negative and especially Gram-positive bacterial growth. These molecules are proof-of-principle of a class of compounds with novel activities, which may in the future be developed into a new class of antibiotics that will expand the available choices for therapy against drug-resistant bacteria.     

Thermokinetic study of CODA azoic liquid crystal and thin films deposition by matrix-assisted pulsed laser evaporation

Azoic dyes are compounds of interest from the point of view of their potential applications, such as the use of liquid crystals in optoelectronic and organic electroluminescent devices, or may be employed as template matrices for producing high-aspect ratio inorganic nanomaterials. Herein, 4-[(4-chlorobenzyl)oxy]-3,4′-dichloroazobenzene azoic dye, known as CODA, is selected as a choice compound among such materials due to its liquid crystalline properties and may be further used as nanostructured material in various applications. Thermokinetic study of CODA azoic dye thermal decomposition in air flow atmosphere was performed by employing thermogravimetric data; the kinetic parameters of the two decomposition steps were obtained under non-isothermal linear regimes, by means of multi-heating rates methods. Differential and integral “model-free” kinetic methods like Friedmann, Kissinger–Akahira–Sunose and Ortega, the invariant kinetic parameters method and the Perez-Maqueda et al. criterion (by Coats–Redfern and differential equations) were used. The kinetic study reveals very different behaviour related to the two decomposition steps of CODA, with complex processes composed of more than one kinetic mechanism for each of those, as indicated also by the Gotor et al. master plot method. Modern devices incorporating such materials tend to use them as thin films due to their specific properties; the CODA thin films were deposited on silicon substrates by matrix-assisted pulsed laser evaporation technique, using a Nd:YAG laser working at the wavelength of 266 nm. The preservation of the CODA compound after the transfer on the substrates was confirmed by Fourier transform infrared spectroscopy, while the morphology and topography of the deposited materials and of the thin film surfaces were investigated by atomic force microscopy and optical microscopy.     

Optical and electrochemical-mediated detection of ascorbic acid using manganese porphyrin and its gold hybrids

The developments concerning new hybrids based on porphyrin derivatives and colloids destined for the detection of ascorbic acid (AA) in the relevant range for medical investigations are presented. Mn(III) tetratolylporphyrin chloride (MnTTPCl), spherical gold colloid (n-Au), and their hybrid (MnTTPCl/n-Au) were chosen to be comparatively investigated by ultraviolet–visible spectroscopy in the presence of AA. The hybrid material (MnTTPCl/n-Au) has the best capacity to detect concentrations of AA in the range of 2.6 × 10^?6–4.38 × 10^?5 M. Modified glassy carbon (GC) electrodes were obtained by thin film deposition of MnTTPCl, n-Au alone, and in successive mixed thin films, comparing their response during the electrochemical oxidation of AA. The electrocatalytic effect of the MnTTPCl on the AA oxidation is justified both by the increase in the peak current density and by the shift toward more negative potentials (0.024 V). The GC/MnTTPCl electrode has the best electrocatalytic effect for the AA oxidation and is promising for sensor applications.     

Master–slave synchronization of Lorenz systems using a single controller

A single controller for synchronization of two Lorenz systems is obtained by using Lyapunov function. Numerical results are given for the all three cases with one controller in each equation. Controller contains two or three variables of the master system.     

Quasi-relative interior-type constraint qualifications ensuring strong Lagrange duality for optimization problems with cone and affine constraints

In this article we provide weak sufficient strong duality conditions for a convex optimization problem with cone and affine constraints, stated in infinite dimensional spaces, and its Lagrange dual problem. Our results are given by using the notions of quasi-relative interior and quasi-interior for convex sets. The main strong duality theorem is accompanied by several stronger, yet easier to verify in practice, versions of it. As exemplification we treat a problem which is inspired from network equilibrium. Our results come as corrections and improvements to Daniele and Giuffré (2007) [9].     

The synthesis of multi-walled carbon nanotubes (MWNTs) by catalytic pyrolysis of the phenol-formaldehyde resins

A series of carbon nanomaterials, particularly multi-walled carbon nanotubes (MWNT), are obtained as products from catalytic pyrolysis of the cross-linked phenol-formaldehyde resins with different ferrocene under inert atmosphere. The morphology and structure of the samples were evaluated by TEM and XRD techniques. CNTs morphology is dependent on the iron nanoparticles and their forms (Fe, Fe₃C) resulted from ferrocene decomposition. The amount of nanotubes increases with iron content released from ferrocene catalyst during the pyrolysis process. Fe₃C nanoparticles drive the nucleation and the growth of carbon nanotubes during the pyrolysis process. Long (up to microns) well-defined MWNTs with small defects, ropes and disordered carbon are representatives in the pyrolyzed resins composition.