Ferrole-type compounds containing thiophenic or thiepinic rings in the 3,4-positions of the metallacycle

The new ferrole Fe₂(CO)₆[μ-η²,η⁴-(Fc)CC{C(H)C(R)S}CC(SiMe₃)] [R = SiMe₃ (1) and R = Fc (2)] and ruthenoles Ru₂(CO)₆[μ-η²,η⁴-(Me₃Si)CC{SC(Fc)C(H)}CC(Fc)] 3 and Ru₂(CO)₆[μ-η²,η⁴-(Me₃Si)CC(SCCFc)C(H)C(Fc)] 4, have been obtained from the reactions of M₃(CO)₁₂ (M = Fe, Ru) and FcCCSCCSiMe₃ through S-C bond activations and C-C coupling reactions. Thermolysis of Ru₂(CO)₆[μ₃-η²,η⁴,η³-(Me₃Si)CC{SC(Fc)C(SCCSiMe₃}Ru(CO)₃}CC(Fc)] alone and in the presence of HCCFc, yielded the compounds Ru₂(CO)₆[μ-η²,η⁴-(Me₃Si)CC{SC(Fc)C(SCCSiMe₃)}CC(Fc)] 5 and Ru₂(CO)₆[μ-η²,η⁴-(Me₃Si)CC{SC(Fc)C(SCCSiMe₃)C(H)C(Fc)}CC(Fc)] 6, respectively. The crystal structures of the compounds 1, 3, 4 and 6 are reported.     

Titania–Silica Materials for Enhanced Photocatalysis

Mesoporous titania–organosilica nanoparticles comprised of anatase nanocrystals crosslinked with organosilica moieties have been prepared by direct co‐condensation of a titania precursor, tetrabuthylortotitanate (TBOT), with two organosilica precursors, 1,4‐bis(triethoxysilyl) benzene (BTEB) and 1,2‐bis(triethoxysilyl) ethane (BTEE), in mild conditions and in the absence of surfactant. These hybrid materials show both high surface areas (200–360 m² g^?1) and pore volumes (0.3 cm³ g^?1) even after calcination, and excellent photoactivity in the degradation of rhodamine 6G and in the partial oxidation of propene under UV irradiation, especially after the calcination of the samples. During calcination, there is a change in the Ti^IV coordination and an increase in the content of Si?O?Ti moieties in comparison with the uncalcined materials, which seems to be responsible for the enhanced photocatalytic activity of hybrid titania–silica materials as compared to both uncalcined samples and the control TiO₂.     

Highly Stereoselective [4+2] and [3+2] Spiroannulations of 2‐(2‐Oxoindolin‐3‐ylidene)acetic Esters Catalyzed by Bifunctional Thioureas

A new Michael–Michael cascade reaction between 2‐(2‐oxoindolin‐3‐ylidene)acetic esters 1 and nitroenoates 2 , catalyzed by bifunctional thioureas, is investigated. The combination of the two Michael reactions results in a novel and facile [4+2] or [3+2] spiroannulation process, which is characterized by the following features: 1) two carbon–carbon bonds and four stereocenters, including a quaternary spiro carbon, are formed under mild conditions; 2) an unprecedented and stereochemically defined substitution pattern on the spirocarbocyclic unit is obtained; 3) the double‐bond configuration of the donor–acceptor nitroenoate 2 determines the absolute configuration of the spiro center, whereas the remaining stereocenters are formed under control of the catalyst. The effect on the final stereochemical outcome of structural variations of each starting material, catalyst, and experimental conditions is analyzed in detail. In particular, the use of specifically designed chiral nitroenoates enables diverse polyfunctional spirocyclohexane derivatives containing six consecutive stereogenic centers to be constructed. To our knowledge, this is the first asymmetric organocatalytic strategy enabling both five‐ and six‐membered β‐nitro spirocarbocyclic oxindoles.     

Analytical approach for monitoring endocrine-disrupting compounds in urban waste water treatment plants

The presence of endocrine-disrupting compounds in influent and effluent water samples from four waste water treatment plants located in Italy was studied. The estrogen-like activity of the water samples was measured using a chemiluminescent recombinant yeast assay which is based on genetically engineered yeast cells that express the human estrogen receptor. This receptor, once activated, elicits the expression of the reporter gene lac-Z and, consequently, the production of β-galactosidase, which is then measured by chemiluminescence. To control and minimize sample matrix effects, an external control based on a modified yeast strain stably expressing β-galactosidase was developed and also used in the assay. Rapid and sensitive chemiluminescent enzyme immunoassays were also developed and validated for the quantification of 17β-estradiol, estrone, and estriol in waste water samples. Results from both methods were compared with a reference high-performance liquid chromatography and electrospray ionization tandem mass spectrometry (HPLC ESI-MS-MS) method developed for the quantification of natural estrogens. The recombinant yeast assay revealed a significant estrogenic activity in the influent samples, ranging from 80 to 400 pmol/L 17β-estradiol equivalents (EEQ), which was reduced by 70–95 % in the effluent samples. The yeast assay also showed a systematic 20–30 % overestimation of estrogenic activity relative to the HPLC ESI-MS-MS method, suggesting the presence of other compounds in the samples with estrogenic activity. The chemiluminescent enzyme immunoassays showed the presence of estrogens in the influent samples (mean concentrations: 350–450 pmol/L for estrone, 5–100 pmol/L for 17β-estradiol, 25–300 pmol/L for estriol), with significantly lower concentrations detected in the respective effluent samples. The waste water treatment was able to reduce natural estrogen concentrations by 40–95 %, although a high variability was observed. The enzyme immunoassay data correlated well with data obtained by the HPLC ESI-MS-MS method. Although the recombinant yeast assay represents a useful tool for a first-level screening of estrogenic activity due to its simplicity and high analytical throughput, sample matrix effects observed in waste water of industrial origin were found to strongly affect the yeast cells response, even when properly corrected for using the external control, thereby limiting its use to urban waste water. Its integration with chemiluminescent enzyme immunoassays would improve its performance by reducing false negative results, thereby enabling its use in extensive studies monitoring for the presence of endocrine-disrupting compounds in urban treatment plant effluents.     

Assessment of Inorganic Fibre Burden in Biological Samples by Scanning Electron Microscopy – Energy Dispersive Spectroscopy

A method based on cloud point extraction (CPE) separation/preconcentration of trace cadmium as a prior step to its determination by graphite furnace atomic absorption spectrometry (GFAAS) has been developed. If the system temperature is higher than the cloud point temperature (CPT) of the nonionic surfactant of p-octyl polyethyleneglycolphenyether (Triton X-100), the complex of Cd²⁺ with 1-(2-pyridylazo)-2-naphthol (PAN) could be extracted into surfactant-rich phase. The chemical variables affecting CPE were evaluated and optimized. Under the optimum conditions, preconcentrating 10.0 mL of water samples permitted a limit of detection of 5.9 ng · L⁻¹ (3σ) for cadmium with an enhancement factor of 50 and a relative standard deviation of 2.1% (n = 11, c = 2.0 ng · mL⁻¹). The method was applied to the determination of cadmium in reference material and water samples with satisfactory results.     

Cavitand‐Grafted Silicon Microcantilevers as a Universal Probe for Illicit and Designer Drugs in Water

The direct, clean, and unbiased transduction of molecular recognition into a readable and reproducible response is the biggest challenge associated to the use of synthetic receptors in sensing. All possible solutions demand the mastering of molecular recognition at the solid–liquid interface as prerequisite. The socially relevant issue of screening amine‐based illicit and designer drugs is addressed by nanomechanical recognition at the silicon–water interface. The methylamino moieties of different drugs are all first recognized by a single cavitand receptor through a synergistic set of weak interactions. The peculiar recognition ability of the cavitand is then transferred with high fidelity and robustness on silicon microcantilevers and harnessed to realize a nanomechanical device for label‐free detection of these drugs in water.     

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.     

Comparison of different calibration methods for the determination by FT-NIR spectroscopy of the hydroxyl number in polyester resins

Different calibration methods have been applied for the determination of the Hydroxyl Number in polyester resins, namely Partial Least Squares (PLS), Principal Component Regression (PCR), Ordinary Least Squares with selection of the variables by genetic algorithm (OLS-GEN) and back-propagation Artificial Neural Networks (BP-ANN). The predictive ability of the regression models was estimated by splitting the dataset in training and test sets by application of the Kohonen self-organising maps. The linear methods (OLS-GEN, PLS and PCR) showed comparable results while artificial neural networks provided the best results both in fitting and prediction.     

Magnetic properties of nanocrystalline CoPt electrodeposited films. Influence of P incorporation

Platinum-rich CoPt films have been electrodeposited with the aim of preparing hard magnetic films on silicon-based substrates without the need for subsequent annealing. Electrodeposition conditions have permitted the crystalline structure of the films to be controlled. Pt percentages of up to 60–65 wt.% have been attained while maintaining the hexagonal Co phase, leading to CoPt films with moderate coercivity and good corrosion resistance. However, when low deposition potentials were used, CoPt films with higher Pt percentages were obtained, but in this case, the films exhibited an fcc structure, having lower coercivity and less corrosion resistance. The presence of hypophosphite in the solution limited the platinum percentage in the deposited CoPtP films, but an hexagonal close-packed (hcp) structure was always observed in this case. The incorporation of P into the deposits led to increases in both the coercivity of the films and the corrosion resistance of the coatings, with respect to pure CoPt. The highest coercivity was obtained for hcp CoPtP deposits with 40 wt.% of Pt.     

Analysis of wine phenolics by high-performance liquid chromatography using a monolithic type column

A polyacrylamide gel crosslinked with allyl-β-cyclodextrin can be used repeatedly for several weeks for the separation of DNA fragments, since bubbles are not generated during a run. Allyl-β-cyclodextrin can easily be synthesized in one step from allylglycidylether and β-cyclodextrin. The plate numbers for DNA fragments, up to about 1500 bp, are high: for the separation of pBR322/HaeIII fragments they were in the range 450 000–1 600 000 m⁻¹. The resolution was almost independent of the concentration of the crosslinker (allyl-β-cyclodextrin) — in sharp contrast to gels crosslinked with N,N′-methylenebisacrylamide.