The preparation and characterization of trans-platinum(IV) complexes with unusually high cytotoxicity

The physical and biological properties have been determined for three Pt(IV) complexes with trans amine ligands: trans,trans,trans-[PtCl(2)(OH)(2)(dimethylamine)(isopropylamine)] (1(IV)), trans,trans,trans-[PtCl(2)(OH)(2)(dimethylamine)(methylamine)] (2(IV)) and trans,trans,trans-[PtCl(2)(OH)(2)(isopropylamine)(methylamine)] (3(IV)). The crystal structures of 2(IV) and 3(IV) reveal substantial strain resulting from repulsion between the amine ligands and the chlorido and hydroxido ligands. All three complexes have reduction potentials in the range -666 to -770 mV, values usually associated with high resistance to reduction and low cytotoxicity. However, the complexes all demonstrate surprisingly high cytotoxicity with values and trends that closely follow those seen for the Pt(II) congeners of these complexes. These results are consistent with more rapid reduction of the Pt(IV) complexes than would be expected based on the reduction potentials, perhaps associated with the trans arrangement of the chlorido ligands.     

Analysis of perfluorinated alkyl substances in Spanish sewage sludge by liquid chromatography-tandem mass spectrometry

The present article describes the development of an analytical method for the determination of 13 perfluorinated alkyl substances (PFAS), as well as its application to real sewage sludge samples to confirm the presence of these compounds. The isolation of the analytes was performed by agitation, sonication and centrifugation techniques, followed by EnviCarb cleanup and weak anion exchange solid-phase extraction. Sensitive and selective determination was carried out by high-performance liquid chromatography?Ctandem mass spectrometry (HPLC-MS/MS). Six mass-labelled internal standards were used to ensure the accuracy of the analytical results following isotopic dilution method. Several mobile phases (acetonitrile, methanol, mixtures of both and water with ammonium acetate or acetic acid) have been tested to reach the best resolution and reproducibility results. Other parameters related to MS/MS conditions were optimized. The reliability of the method was confirmed by the evaluation of linearity (R ²?=?0.995?C0.999), accuracy (84?C99%) and injection repeatability and reproducibility (relative standard deviation below 19 and 23%, respectively). Limits of detection ranged from 0.007 to 2.217?pg. Recoveries show values higher than 80% for most of the target compounds. The application of this method to twenty real samples demonstrates its efficiency and accuracy, as well as provides for the first time to our knowledge, PFAS levels in sewage sludges from Spain.

Characterization of galactooligosaccharides derived from lactulose

Galactooligosaccharides are non-digestible carbohydrates with potential ability to modulate selectively the intestinal microbiota. In this work, a detailed characterization of oligosaccharides obtained by transgalactosylation reactions of the prebiotic lactulose, by using β-galactosidases of different fungal origin (Aspergillus oryzae, Aspergillus aculeatus and Kluveromyces lactis), is reported. Oligosaccharides of degree of polymerization (DP) up to 6 were detected and quantified by HPLC-ESI MS from a complex mixture produced by transgalactosylation reaction with A. oryzae (GOSLuAo), whereas only carbohydrates up to DP4 and DP5 were found for those obtained from the reaction with β-galactosidases from K. lactis (GOSLuKl) and A. aculeatus (GOSLuAa), respectively. Disaccharides (galactosyl-galactoses and galactosyl-fructoses) and trisaccharides were characterised in the three mixtures by GC-MS as their trimethylsilyl oximes. Galactosyl- and digalactosyl-glycerols were produced during the transgalactosylation reaction of lactulose with β-galactosidases from A. aculeatus and K. lactis, due to the presence of glycerol as enzyme stabiliser.     

Monte Carlo and event-driven dynamics of Brownian particles with orientational degrees of freedom

Recently, a simple scaling argument was introduced that allows us to map, with some precautions, Brownian and Monte Carlo dynamics for spherical particles. Here, we extend the scaling to study systems that have orientational degrees of freedom and carefully asses its validity over a wide region of temperature and density. Our work allows us to devise a Brownian Monte Carlo algorithm that produces, to a good approximation, physically meaningful trajectories with a minimum programming effort, although at the expense of some sampling efficiency.     

Harmonic generation in ablation plasmas of wide bandgap semiconductors

Third and fifth harmonic generation of an IR (1.064 μm) pulsed laser has been produced in ablation plasmas of the wide bandgap semiconductors CdS and ZnS. The study of the temporal behaviour of the harmonic emission has revealed the presence of distinct compositional populations in these complex plasmas. Species ranging from atoms to nanometre-sized particles have been identified as emitters, and their nonlinear optical properties can be studied separately due to strongly differing temporal behaviour. At short distances from the target (<1 mm), atomic species are mostly responsible for harmonic generation at early times (<500 ns), while clusters and nanoaggregates mostly contribute at longer times (>1 μs). Harmonic generation thus emerges as a powerful and universal technique for ablation plasma diagnosis and as a tool to determine the nonlinear optical susceptibility of ejected clusters or nanoparticles.     

Nitrogen/gold codoping of the TiO2(101) anatase surface. A theoretical study based on DFT calculations

The interaction between implanted nitrogen atoms, adsorbed gold atoms, and oxygen vacancies at the anatase TiO(2)(101) surface is investigated by means of periodic density functional theory calculations. Substitutional and interstitial configurations for the N-doping have been considered, as well as several adsorption sites for Au adatoms and different types of vacancies. Our total energy calculations suggest that a synergetic effect takes place between the nitrogen doping on one hand and the adsorption of gold and vacancy formation on the other hand. Thus, while pre-implanted nitrogen increases the adsorption energy for gold and decreases the energy required for the formation of an oxygen vacancy, pre-adsorbed gold or the presence of oxygen vacancies favors the nitrogen doping of anatase. The analysis of the electronic structure and electron densities shows that a charge transfer takes place between implanted-N, adsorbed Au and oxygen vacancies. Moreover, it is predicted that the creation of vacancies on the anatase surface modified with both implanted nitrogen and supported gold atoms produces migration of substitutional N impurities from bulk to surface sites. In any case, the most stable configurations are those where N, Au and vacancies are close to each other.     

Industriall Control of the Filtration in the Beer Manufacturing Process

In the aim to improve the filtration process in the beer ma nufacture, a study on the beer turbidity have been made using two different techniques: nephelometry and V-UV spectrometry. Even though the former is the most commonly used, we propose the use of V-UV spectrometry since it is possible to follow the performace - of all the filtration line, not only in a punctual way but in a - wide range of wavelenghts. From the results of this work we deduce that V-UV spectrometry offers a better quality of results than nephelometry, being more useful in rutin periodic controls.     

Effects of high pressure on unsaturated fatty acids

The objective of this study is to investigate the effects of high pressure processing on the molecular structure of some unsaturated fatty acids. Samples of elaidic acid, linoleic acid, ZE and EE conjugated linoleic acid are treated at 293 or 333?K at pressures up to 700?MPa. It is observed that the adiabatic heat generated from compression is able to bring the sample temperature above 373?K after 700?MPa. These relatively extreme conditions are of great interest for food sterilization, but they may induce undesirable change in fatty acid quality characteristics. To check for structural changes, Raman spectra of the samples are analysed after treatments. The comparison with Raman spectra of samples kept at atmospheric pressure shows that pressure induces some conformational changes at the hydrocarbon skeleton in solid samples, while the liquid ones remain unchanged. No cis/trans isomerization occurs, but gauche conformers are likely to be present.     

Compositional changes induced by 3.5 keV Ar ion bombardment in Ni-Ti oxide systems A comparative study

Compositional changes induced by 3.5 keV Ar⁺ sputtering in TiO₂, NiO, NiTiO₃ and a (TiO₂ + NiO) mixture have been quantitatively studied by XPS. Although all the samples show important changes in their stoichiometry, the extent of the decomposition depends on the compound. The stability of Ti⁴⁺ appears to be enhanced by the presence of Nisu2+ cations which, on the other hand, are more easily reduced to Ni⁰ than in pure NiO. To explain these results a redox solid state reaction between the intermediate phases formed during sputtering is proposed, which tends to preserve the most stable phases.