Dinuclear amine-thiophenolate complexes coligated by ferrocenemonocarboxylate and 1,1'-ferrocenedicarboxylate anions: preparation, characterization and structures of trinuclear [LMII 2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII 2)2(O2CC5H4)2Fe]2+ complexes (M=Co, Ni, Zn)

A series of novel tri- and pentanuclear complexes composed of dinuclear LM(2) units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaazadithiophenolate ligand) and ferrocenecarboxylate ([CpFeC(5)H(4)CO(2)](-)) or 1,1'-ferrocenedicarboxylate ([Fe(C(5)H(4)CO(2))(2)](2-)) groups is reported. The complexes [LM(II) (2)(O(2)CC(5)H(4)FeCp)](+) (M=Co (6), Ni (7), Zn (8)) and [(LM(II) (2))(2)(O(2)CC(5)H(4))(2)Fe](2+) (M=Co (9), Ni (10)) have been prepared by substitution reactions from labile [LM(II) (2)L'](+) precursors (L'=Cl, OAc) and the respective ferrocenecarboxylate anions in methanol. Mixed-valent [(LCo(II)Co(III))(2)(O(2)CC(5)H(4))(2)Fe](4+) (11) was prepared by oxidation of 9 with bromine. Complexes 7[BPh(4)], 8[BPh(4)], 9[BPh(4)](2), 10[BPh(4)](2), and 11[ClO(4)](4) have been characterized by X-ray crystallography; showing that the ferrocenyl carboxylates act as bidentate (7, 8) or bis-bidentate (9-11) bridging ligands towards one or two bioctahedral LM(2) subunits, respectively. The structures are retained in solution as indicated by NMR spectroscopic studies on the diamagnetic Zn(2)Fe complex 8[ClO(4)]. Electrochemical studies reveal significant anodic potential shifts for the oxidation potential of the ferrocenyl moieties upon complexation and the magnitude of the potential shift appears to correlate with the charge of the LM(2) subunits. This is qualitatively explained in terms of destabilizing electrostatic (Coulomb) interactions between the M(2+) ions of the LM(2) unit and the proximate ferrocenium fragment. An analysis of the temperature-dependent magnetic susceptibility data for 10[BPh(4)](2) shows the presence of weak ferromagnetic magnetic exchange interactions between the Ni(II) ions in the LNi(2) units. The exchange coupling across the ferrocenedicarboxylate bridge is negligible.     

High-Field Electron Paramagnetic Resonance Reveals a Stable Glassy Fraction up to Melting in Semicrystalline Poly(dimethylsiloxane)

The reorientation of the guest 4-methoxy-TEMPO (spin probe) in the disordered fraction of semicrystalline poly(dimethylsiloxane) (PDMS) is investigated by high-field electron paramagnetic resonance (HF-EPR) at 190 and 285 GHz. Accurate numerical simulations of the HF-EPR lineshapes evidence that the reorientation times of the spin probes are distributed between the melting temperature \(T_{\rm m}\) and \(T_{\rm m}\)—30 K. The distribution exhibits, in addition to a broad component, a narrow component with low mobility up to the PDMS melting point. It is shown that the temperature dependence of the reorientation time of the spin probes with low mobility is the same of the spin probes in glassy PDMS. The result suggests that the low-mobility fraction is localized in the so-called rigid amorphous fraction.     

A Class of Integrable Flows on the Space of Symmetric Matrices

For a given skew symmetric real n × n matrix N, the bracket [X, Y] _N = XNY − YNX defines a Lie algebra structure on the space Sym(n, N) of symmetric n × n real matrices and hence a corresponding Lie-Poisson structure. The purpose of this paper is to investigate the geometry, integrability, and linearizability of the Hamiltonian system , or equivalently in Lax form, the equation on this space along with a detailed study of the Poisson geometry itself. If N has distinct eigenvalues, it is proved that this system is integrable on a generic symplectic leaf of the Lie-Poisson structure of Sym(n, N). This is established by finding another compatible Poisson structure. If N is invertible, several remarkable identifications can be implemented. First, (Sym(n, N), [·, ·]) is Lie algebra isomorphic with the symplectic Lie algebra associated to the symplectic form on given by N ⁻¹. In this case, the system is the reduction of the geodesic flow of the left invariant Frobenius metric on the underlying symplectic group Sp(n, N ⁻¹). Second, the trace of the product of matrices defines a non-invariant non-degenerate inner product on Sym(n, N) which identifies it with its dual. Therefore Sym(n, N) carries a natural Lie-Poisson structure as well as a compatible “frozen bracket” structure. The Poisson diffeomorphism from Sym(n, N) to maps our system to a Mischenko-Fomenko system, thereby providing another proof of its integrability if N is invertible with distinct eigenvalues. Third, there is a second ad-invariant inner product on Sym(n, N); using it to identify Sym(n, N) with itself and composing it with the dual of the Lie algebra isomorphism with , our system becomes a Mischenko- Fomenko system directly on Sym(n, N). If N is invertible and has distinct eigenvalues, it is shown that this geodesic flow on Sym(n, N) is linearized on the Prym subvariety of the Jacobian of the spectral curve associated to a Lax pair formulation with parameter of the system. If, on the other hand, N has nullity one and distinct eigenvalues, in spite of the fact that the system is completely integrable, it is shown that the flow does not linearize on the Jacobian of the spectral curve. Research partially supported by NSF grants CMS-0408542 and DMS-0604307. Research partially supported by the Swiss SCOPES grant IB7320-110721/1, 2005-2008, and MEdC Contract 2-CEx 06-11-22/25.07.2006. Research partially supported by the California Institute of Technology and NSF-ITR Grant ACI-0204932. Research partially supported by the Swiss NSF and the Swiss SCOPES grant IB7320-110721/1.     

A common fixed point theorem for compatible quasi contractive self mappings in metric spaces

A common fixed point theorem for weakly commuting quasi contractive self mappings with contracting orbital diameters in metric spaces [V. Berinde, A common fixed point theorem for quasi contractive type mappings, Ann. Univ. Sci. Budapest. 46 (2003) 81-90] is extended to the more general class of compatible quasi contractive self mappings. Our result does extend and generalize numerous related results in literature.     

Polarization-controlled switching between diffraction orders in transverse-periodically aligned nematic liquid crystals

Transverse-periodic-oriented nematic liquid crystals (LCs) are a special type of optical axis grating that are capable of very high efficiency diffraction (theoretically, 100%) in thin layers of materials with thickness comparable to the radiation wavelength. In particular, they fully diffract linearly polarized input beam into circularly polarized +1st and -1st diffraction orders. We experimentally demonstrate switching between diffraction orders of such gratings when the polarization of the incident beam changes from right-circular to left-circular and vice versa with the aid of an electrically controlled LC phase retarder. Such a setup in which the diffraction efficiency and direction are controlled externally, without application of an electric field to the transverse-periodic grating, provides additional control opportunities and does not compromise the quality of the grating. The grating used in the experiment was 1.5 microm thick and had a period of 4 microm. The contrast ratio of switching between the +1st and -1st orders was as high as 267:1 for a He-Ne laser beam with a switching time of 6.6 ms.     

Poly(alkylene-H-phosphonate)s obtained by direct esterification and oxidation of hypophosphorous acid with ethylene glycol

This paper presents for the first time the synthesis of poly(alkylene-H-phosphonate)s by one-pot tandem reaction of hypophosphorous acid and ethylene glycol. Zirconium oxychloride was used as esterification catalyst, Nickel vinylphosphonate, Nickel sulfate, Nickel chloride hexahydrate were used as transfer hydrogenation catalyst. Nickel vinylphosphonate was synthesized in our laboratory and used for the first time as catalyst in this process. The compounds were characterized by ¹H-NMR, ¹³C-NMR and ³¹P-NMR spectroscopy. Molar masses were determined by SEC-MALLS technique and depend on the catalyst used. The obtained poly(alkylene-H-phosphonate)s have molar masses between 1.50 and 11.85 kDa, higher than those obtained by other methods mentioned in the literature.     

Polylactic acid (PLA)/Silver-NP/VitaminE bionanocomposite electrospun nanofibers with antibacterial and antioxidant activity

The antibacterial property of silver nanoparticles (Ag-NPs) and the antioxidant activity of Vitamin E have been combined by incorporation of these two active components within polylactic acid (PLA) nanofibers via electrospinning (PLA/Ag-NP/VitaminE nanofibers). The morphological and structural characterizations of PLA/Ag-NP/VitaminE nanofibers were performed by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy and X-ray diffraction. The average fiber diameter was 140 ± 60 nm, and the size of the Ag-NP was 2.7 ± 1.5 nm. PLA/Ag-NP/VitaminE nanofibers inhibited growth of Escherichia coli, Listeria monocytogenes and Salmonella typhymurium up to 100 %. The amount of released Ag ions from the nanofibers immersed in aqueous solution was determined by Inductively Coupled Plasma Mass Spectrometry, and it has been observed that the release of Ag ions was kept approximately constant after 10 days of immersion. The antioxidant activity of PLA/Ag-NP/VitaminE nanofibers was evaluated according to DPPH (2,2-diphenyl-1-picrylhydrazyl) method and determined as 94 %. The results of the tests on fresh apple and apple juice indicated that the PLA/Ag/VitaminE nanofiber membrane actively reduced the polyphenol oxidase activity. The multifunctional electrospun PLA nanofibers incorporating Ag-NP and Vitamin E may be quite applicable in food packaging due to the extremely large surface area of nanofibers along with antibacterial and antioxidant activities. These materials could find application in food industry as a potential preservative packaging for fruits and juices.     

Fluorescent Flavin/PVP-Coated Silver Nanoparticles: Design and Biological Performance

A red-emitting fluorescent Riboflavin (RF)/Polyvinylpyrrolidone (PVP)-coated silver nanoparticles system, λ_em?=?527 nm, Φ?=?0.242, with a diameter of the metallic core of 27.33 nm and a zeta potential of ? 25.05 mV was prepared and investigated regarding its biological activity. We found that PVP has a key role in RF adsorption around the SNPs surface leading to an enhancement of antioxidant properties (～70%), low cytotoxicity (> 90% cell viability, at 50 µL/mL, after 48 h of incubation) as well as to an efficient process of its cellular uptake (～ 60%, after 24 h of incubation) in L929 cells. The results are relevant concerning the involvement of RF and its coenzymes forms in SNPs - based systems, in cellular respiration as well as for future studies as antioxidant marker system on tumoral cells for viewing and monitoring them, by cellular imaging.

     

Vanadium bromoperoxidase-coupled fluorescent assay for flow cytometry sorting of glucose oxidase gene libraries in double emulsions

A Vanadium bromoPeroxidase-coupled fluorescent assay (ViPer) for ultrahigh-throughput screening of glucose oxidase (GOx) gene libraries employing double emulsions and flow cytometry was developed. The assay is based on detection of the product of a GOx reaction, hydrogen peroxide, that is first converted to a hypobromide by vanadium bromoperoxidase in the presence of sodium bromide. The hypobromide is afterwards detected in a reaction with a fluorogenic probe, 3-carboxy-7-(4'-aminophenoxy)-coumarine, where fluorescent 3-carboxy-coumarine is released. The ViPer screening system is three times more sensitive than a horseradish peroxidase coupled detection system and more resistant to bleaching of fluorescence in excess of peroxide. Using the ViPer screening system a high epPCR gene library containing 100,000 different GOx variants was screened for active clones in less than 1 h by flow cytometry. A library containing 0.15% of yeast cells expressing active enzyme variants and with an average GOx activity in the liquid culture of 0.47 U/mL, after one round of sorting, had 28.12% of the yeast cells expressing the active GOx (an enrichment factor of 200) and 26.8 U/mL of the GOx activity in the liquid culture (an enrichment factor of 57). The developed screening system could be adapted and used in a directed evolution of GOx and other hydrogen peroxide-producing enzymes (oxidases) and glycosidases if coupled with a carbohydrate oxidase.