Synthesis,characterization and assessment of the cytotoxic activity of Cu(II), Fe(III) and Mn(III) complexes of camphoric acid‐derived salen ligands

Novel Cu(II), Fe(III) and Mn(III) salen‐type metal complexes from (1R,3S)‐N,N′‐bis[salicylidene]‐1,3‐diamino‐1,2,2‐trimethylcyclopentane were synthesized and screened for their in vitro cytotoxic activity against three human cancer cell lines: melanoma, colorectal and breast. In vitro experiments carried out with the three metal complexes show that the copper complex exhibits the highest cytotoxic activity towards all cell lines studied, presenting IC₅₀ values of 3.32–6.71 μM. A significant improvement in the anti‐proliferative effect, by 20‐fold, is observed with this complex when compared with conventional chemotherapy. The relationship between structure, redox characteristics and biological activity in human cancer cell lines was evaluated for the most efficient Cu(II) complex and associated with theoretical calculations. Copyright © 2015 John Wiley & Sons, Ltd.     

Shear horizontal (SH) ultrasound wave propagation around smooth corners

Shear horizontal (SH) ultrasound guided waves are being used in an increasing number of non-destructive testing (NDT) applications. One advantage SH waves have over some wave types, is their ability to propagate around curved surfaces with little energy loss; to understand the geometries around which they could propagate, the wave reflection must be quantified. A 0.83 mm thick aluminium sheet was placed in a bending machine, and a shallow bend was introduced. Periodically-poled magnet (PPM) electromagnetic acoustic transducers (EMATs), for emission and reception of SH waves, were placed on the same side of the bend, so that reflected waves were received. Additional bending of the sheet demonstrated a clear relationship between bend angles and the reflected signal. Models suggest that the reflection is a linear superposition of the reflections from each bend segment, such that sharp turns lead to a larger peak-to-peak amplitude, in part due to increased phase coherence.     

Supercritical hydrogen adsorption in nanostructured solids with hydrogen density variation in pores

Experimental excess isotherms for the adsorption of gases in porous solids may be represented by mathematical models that incorporate the total amount of gas within a pore, a quantity which cannot easily be found experimentally but which is important for calculations for many applications, including adsorptive storage. A model that is currently used for hydrogen adsorption in porous solids has been improved to include a more realistic density profile of the gas within the pore, and allows calculation of the total amount of adsorbent. A comparison has been made between different Type I isotherm equations embedded in the model, by examining the quality of the fits to hydrogen isotherms for six different nanoporous materials. A new Type I isotherm equation which has not previously been reported in the literature, the Unilan-b equation, has been derived and has also been included in this comparison study. These results indicate that while some Type I isotherm equations fit certain types of materials better than others, the T?th equation produces the best overall quality of fit and also provides realistic parameter values when used to analyse hydrogen sorption data for a model carbon adsorbent.     

Predictions of QCD fragmentation models ine + e − annihilation up to\sqrt s = 200 GeV

Results on event and single particle characteristics are presented for the three most successful perturbative QCD+fragmentation models in the c.m. energy range 12.0≦W≦200 GeV. The models were optimised to describe the properties of the large sample of hadronic events obtained by TASSO atW=35 GeV. The energy evolution of the observables across the range spanned by the PETRA and PEP data, 12.0≦〈W〉≦41.5 GeV, is reasonably well described by all the models. However, for some quantities the predictions of the different models diverge at higher energies; distributions of observables are shown at c.m. energies of 93 and 200 GeV, where data are expected from thee ⁺ e ^? colliders currently under construction. The ability to describe simultaneously, with the same parameter values, hadronic event features both at PETRA/PEP and LEP/SLC energies will provide a severe test of the models. The effects of top quark production on the event properties are illustrated for a top mass of 60 GeV/c². Predictions are given for the rates of multijet events up toW=200 GeV, where ≧4-jet events dominate the cross section and will form a background to events containing heavy states which decay into hadron jets.     

DNA-protein cross-links between guanine and lysine depend on the mechanism of oxidation for formation of C5 vs C8 guanosine adducts

The reaction between N(alpha)-acetyllysine methyl ester (Lys) and 2'-deoxyguanosine (dGuo) was used to study structural aspects of DNA-protein cross-link (DPC) formation. The precise structure of DPCs depended on the nature of the oxidant and cross-linking reactions in which a series of different oxidation conditions generated a distribution of adducts, principally spirodiiminodihydantoins with lysine appended at the purine position of C5 (5-Lys-Sp), C8 (8-Lys-Sp), or both C5 and C8 (5,8-diLys-Sp). Singlet oxygen oxidation of dGuo produced 5-Lys-Sp exclusively when Rose Bengal or methylene blue was used to photochemically generate (1)O2 in the presence of Lys, whereas riboflavin or benzophenone-mediated photochemistry generated lysine radicals and led to C8 adduct formation, yielding 8-Lys-Sp and 5,8-diLys-Sp. Notably, the yield of dGuo modifications from riboflavin photooxidation increased dramatically in the presence of lysine. Oxidation of deoxyguanosine/lysine mixtures with Na2IrCl6 or sulfate radicals produced both 5-Lys-Sp and 8-Lys-Sp. The same adducts were formed in single and double-stranded oligodeoxynucleotides, and these could be analyzed after nuclease digestion. Adduct formation in duplex DNA was somewhat dependent on the accessibility of lysine to C5 vs C8 of the purine. No adduct formation was detected between lysine and the other nucleobases T, C, or A. Overall, the precise location of adduct formation at C5 vs C8 of guanine appears to be diagnostic of the oxidation pathway.     

Cobalt promoted copper manganese oxide catalysts for ambient temperature carbon monoxide oxidation

Low levels of cobalt doping (1 wt%) of copper manganese oxide enhances its activity for carbon monoxide oxidation under ambient conditions and the doped catalyst can display higher activity than current commercial catalysts.     

Investigation of photobleaching and saturation of single molecules by fluorophore recrossing events

A method for investigation of photobleaching and saturation of single molecules by fluorophore recrossing events in a laser beam is described. The diffraction-limited probe volumes encountered in single-molecule detection (SMD) produce high excitation irradiance, which can decrease available signal. The single molecules of several dyes were detected and the data was used to extract interpeak times above a defined threshold value. The interpeak times revealed the number of fluorophore recrossing events. The number of molecules detected that were within 2 ms of each other represented a molecular recrossing for this work. Calcein, fluorescein and R-phycoerythrin were analyzed and the saturation irradiance and photobleaching effects were determined as a function of irradiance. This approach is simple and it serves as a method of optimizing experimental conditions for single-molecule detection.     

The synthesis and characterisation of europium terpyridine-N-oxide complexes

Europium complexes of a series of terpyridine-N-oxide ligands have been prepared and structurally characterised by crystallographic studies. While the addition of three equivalents of terpyridine-1-oxide or terpyridine-1,1'-bisoxide results in complexes with nine co-ordinate tricapped trigonal prismatic or monocapped square antiprismatic geometries, respectively, three equivalents of the terpyridine-1,1',1'-trisoxide yields an unexpected 8 co-ordinate geometry. Luminescence studies of the three complexes in acetonitrile show a typical europium emission spectra, dominated by the (5)D(0)-(7)F(2) transition. While no simple trend in the relative quantum yields could be ascertained, the terpyridine-1-oxide complex was observed to have the most intense luminescence for this set of complexes.     

First CRDS-measurements of water vapour continuum in the 940 nm absorption band

Measurements of near-infrared water vapour continuum using continuous wave cavity ring down spectroscopy (cw-CRDS) have been performed at around 10611.6 and . The continuum absorption coefficients for N₂-broadening have been determined to be and at , and and at , respectively.These results represent the first near-IR continuum laboratory data determined within the complex spectral environment in the 940 nm water vapour band and are in reasonable agreement with simulations using the semiempirical CKD formulation.