Synthesis and structural studies of hydrazino-crown ethers and thermodynamic studies of their interaction with transition,and post-transition metal ions and methyl ammonium ion

Hydrazino-crown ethers have been synthesized in only 3 or 4 steps starting from 1,2-diacetylhydrazine. The X-ray crystal structure of protonated hydrazino-19-crown-7 (2) showed that one of the hydrazino nitrogen atoms was directed outside the ring cavity. A solvent methanol molecule is held in the cavity of the host ligand by three hydrogen bonds involving two hydrogen atoms bonded to nitrogens of the ligand and the alcohol hydrogen of the methanol. The logK values for the interaction of2 with CH₃NH ₊ ³ , Ag⁺, Pb²⁺, and Cd²⁺ were much less than those for the interaction of symmetrical triaza-l8-crown-6 (5) with the same cations. Hydrazino-crown2 reduced silver ions to silver metal when a solution of2 and silver ions in DMSO was allowed to stand for several days.     

Inhibition of Quorum Sensing,Motility and Biofilm Formation of Pseudomonas aeruginosa by Copper Oxide Nanostructures

Quorum sensing (QS) is the communication between bacterial cells governed by their population density and regulated by the genes controlling virulence factors and biofilm formation. Multiple mechanisms of biofilms are resistive to antimicrobial chemotherapy; therefore novel strategies are required to overcome its limitations. Here, we report the effect of various copper oxide nanostructures (CuO-NSs) on quorum sensing inhibition. The two-dimensional CuO-NSs such as interlaced nanodiscs, nanodiscs and leaf-shaped nanosheets are prepared via a simple chemical method. The Quorum sensing inhibition (QSI) activity of all the CuO-NS are examined using reporter strain Chromobacterium violaceum CV026 and Escherichia coli pSB1142. We found that the CuO-interlaced nanodisc structures exhibit better QSI activity than nanodiscs and leaf-shaped sheets. The interlaced nanodisc structures are inhibited various long-chain N-acyl homoserine lactones (AHLs) mediated QS individually and confirmed by other QS-associated phenomena for Pseudomonas aeruginosa, including biofilm inhibition, inhibition of virulence factors such as pyocyanin, protease production and swarming motility. Thus QSI activity of CuO-NSs is solely dependent on specific shape offering large surface area and more active sites. The CuO-NS is effective quorum sensing inhibitors, which has potential clinical applications in the management of P. aeruginosa associated infections.

     

Interaction of UV Light-Induced α–Tocopherol Radicals with Lipids Detected by an Electron Spin Resonance Prooxidation Effect

The reaction rate constants of the interaction between light-induced α–tocopherol radicals with unsaturated lipids in a heterogeneous system compared to a homogeneous system are of the same order of magnitude. The decay rates of compartmentalized -α-tocopherol radicals were significantly reduced by using negatively charged sodium dodecyl sulfate (SDS) micelles. A partially resolved electron spin resonance (ESR) hyperfine structure was observed under the conditions of both high lipid concentrations in comparison to the α-tocopherol concentration and of a regular distribution of α-tocopherol molecules inside the heterogeneous lipid structures. Alphα-to-copherol radicals have a considerable prooxidation potential at higher concentrations. Ascorbic acid dissolved in the aqueous medium provokes very fast -α-tocopherol radical recycling through the boundary layer between the aqueous medium and micelles. By contrast, very slow reactions such as those of α-tocopherol radicals with glutathione through this boundary layer are measurable. Despite using the heterogeneous SDS micellar system, the decay kinetics of the α-tocopherol radical ESR signal is simply compounded. In addition to the known stabilization effect of cholesterol in membrane systems, cholesterol itself acts as a target molecule attacked by free radicals, e.g. -α-tocopherol radicals. Using stratum corneum extracts that contain unsaturated lipids and cholesterol the -α-tocopherol radical can prooxidatively react with these compounds. Using focused UV light generates a high radical yield in a relatively short time compared to the lifetime of the -α-tocopherol radicals. The decay processes after radical induction can be characterized as consecutive reactions. The compartmentalization of radicals induced in SDS micelles and the close proximity of target molecules are essential if very slow one-electron reductions are to be measured.     

Cellular Uptake of the ATSM−Cu(II) Complex under Hypoxic Conditions

The Cu(II)-diacetyl-bis (N4-methylthiosemicarbazone) complex (ATSM−Cu(II)) has been suggested as a promising positron emission tomography (PET) agent for hypoxia imaging. Several in-vivo studies have shown its potential to detect hypoxic tumors. However, its uptake mechanism and its specificity to various cancer cell lines have been less studied. Herein, we tested ATSM−Cu(II) toxicity, uptake, and reduction, using four different cell types: (1) mouse breast cancer cells (DA-3), (2) human embryonic kidney cells (HEK-293), (3) breast cancer cells (MCF-7), and (4) cervical cancer cells (Hela) under normoxic and hypoxic conditions. We showed that ATSM−Cu(II) is toxic to breast cancer cells under normoxic and hypoxic conditions; however, it is not toxic to normal HEK-293 non-cancer cells. We showed that the Cu(I) content in breast cancer cell after treatment with ATSM−Cu(II) under hypoxic conditions is higher than in normal cells, despite that the uptake of ATSM−Cu(II) is a bit higher in normal cells than in breast cancer cells. This study suggests that the redox potential of ATSM−Cu(II) is higher in breast cancer cells than in normal cells; thus, its toxicity to cancer cells is increased.     

NanoSQUID as magnetic sensor for magnetic nanoparticles characterization

Integrated magnetic sensors based on niobium dc SQUID (Superconducting Quantum Interference Device) for nanoparticle characterizations are presented. The SQUIDs consists of two Dayem bridges of 90 nm × 250 nm and loop area of 4, 1, and 0.55 μm². The devices are realized by using an e-beam lithography nano-fabrication process which can directly pattern the devices in an electron-positive resist and then transferred to a 20 nm single niobium layer by a lift-off post-process. The SQUIDs were designed to have a hysteretic current–voltage characteristic in order to work as a magnetic flux-current transducer. The presence of an integrated niobium coil, tightly coupled to the SQUID, allows us to easily excite the SQUID and to flux bias the SQUID at its optimal working point. Current–voltage characteristics, critical current as a function of the external magnetic field and switching current distributions were performed at liquid helium temperature. A critical current modulation of about 20% and a current-magnetic flux transfer coefficient (responsivity) of 30 μA/Φ₀ have been obtained, resulting in a magnetic flux resolution better than 1 mΦ₀. The authors performed preliminary measurements with and without iron oxide nanoparticles on the SQUID loop in order to show the device sensitivity in view of nano-magnetism applications. It was showed that the presence of magnetic nanoparticles can be easily detected and the magnetic relaxation curve measured.     

Consequences of coarse-grained Vlasov equations

The Vlasov equation is analyzed for coarse-grained distributions resembling a finite width of test particles as used in numerical implementations. It is shown that this coarse-grained distribution obeys a kinetic equation similar to the Vlasov equation, but with additional terms. These terms give rise to entropy production indicating dissipative features due to a nonlinear mode coupling. The interchange of coarse graining and dynamical evolution is discussed with the help of an exactly solvable model for the self-consistent Vlasov equation and practical consequences are worked out. By calculating analytically the stationary solution of a general Vlasov equation we can show that a sum of modified Boltzmann-like distributions is approached dependent on the initial distribution. This behavior is independent of degeneracy and only controlled by the width of test particles. The condition for approaching a stationary solution is derived and it is found that the coarse graining energy given by the momentum width of test particles should be smaller than a quarter of the kinetic energy. Observable consequences of this coarse graining are: (i) spatial correlations in observables, (ii) too large radii of clusters or nuclei in self-consistent Thomas–Fermi treatments, (iii) a structure term in the response function resembling vertex correction correlations or internal structure effects and (iv) a modified centroid energy and higher damping width of collective modes.